Chapter 17

Practice Exercises

17.1 [H3O+] = 12 M

1.0 x 10-14 = [H3O+][OH-] = 12 [OH-]

[OH–] = 8.3 × 10–16 M

17.2 1.00 x 10-14 = [H3O+][OH-]

[H3O+] = 1.00 x 10-14/7.8 x 10-6 = 1.3 x 10-9

The solution is basic

17.3 pOH = 14 – pH = 14 – 4.25 = 9.75

[H3O+] = 10–4.25 = 5.6 × 10–5 M
[OH–] = 10–9.75 = 1.8 × 10–10 M

17.4 pH = –log[H3O+] = –log[3.2 × 10–5] = 4.49

pOH = 14.00 – pH = 14.00 – 4.49 = 9.51

17.5 In general, we have the following relationships between pH, [H+], and [OH–]:
[H3O+] = 10–pH
[H3O+][OH−] = 1.00 × 10–14

(a) [H3O+] = 10–2.90 = 1.3 × 10–3 M

[OH–] = 1.00 × 10–14/1.3 × 10–3 M = 7.7 × 10–12 M
The solution is acidic.
(b) [H3O+] = 10–3.85 = 1.4 × 10–4 M
[OH–] = 1.00 × 10–14/1.4 × 10–4 M = 7.1 × 10–11 M
The solution is acidic.
(c) [H3O+] = 10–10.81 = 1.549 × 10–11 M = 1.6 x 10-11M
[OH–] = 1.00 × 10–14/1.549 × 10–11 M = 6.456 × 10–4 M = 6.5x 10-4M
The solution is basic.
(d) [H3O+] = 10–4.11 = 7.8 × 10–5 M
[OH–] = 1.00 × 10–14/7.8 × 10–5 M = 1.3 × 10–10 M
The solution is acidic.
(e) [H3O+] = 10–11.61 = 2.4 × 10–12 M
[OH–] = 1.00 × 10–14/2.4 × 10–12 M = 4.1 × 10–3 M
The solution is basic.

17.6 [H3O+] = 0.0050 M

pH = –log[H+] = –log[0.0050] = 2.30
pOH = 14.0 – pH = 14.00 – 2.30 = 11.70

17.7 First determine the number of moles of KOH and then the molarity of the solution
 1 mol KOH 
mol KOH = (1.20 g KOH)   = 0.0214 mol KOH
 56.11 g KOH 
0.0214 mol KOH
molarity = = 0.0855 M KOH
0.250 L solution
pOH = –log 0.0855 M = 1.07
pH = 14 – 1.068 = 12.93
[H3O+] = 1.2 × 10–13 M

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17.8 [H3O+] = 10–5.5 = 3.2 × 10–6 M

17.9 (a) HC2H3O2 + H2O
H3O+ + C2H3O2–

[H3O+ ][C2 H3O2 − ]
Ka =
HC2 H3O2 
(b) (CH3)3NH+ + H2O
H3O+ + (CH3)3N
[H3O + ][ ( CH3 )3 N]
Ka =
( CH ) NH + 
 3 3 
(c) H3PO4 + H2O
H3O+ + H2PO4–
[H3O + ][H 2 PO 4 − ]
Ka =
H 3 PO 4 

17.10 (a) HCHO2 + H2O
H3O+ + CHO2–

[H3O + ][CHO2 − ]
Ka =
[ HCHO2 ]
(b) (CH3)2NH2+ + H2O
H3O+ + (CH3)2NH
[H3O+ ][(CH3 ) 2 NH ]
Ka =
 (CH3 ) 2 NH 2 + 
 
(c) H2PO4– + H2O
H3O+ + HPO42–
[H3O + ][HPO4 2− ]
Ka =
 H 2 PO4 − 
 

17.11 The smaller the value of pKa, the stronger the acid.
The acids stronger than acetic acid and weaker than formic acid from Table 17.2 are barbituric acid and
hydrazoic acid..

17.12 The acid with the smaller pKa (HA) is the strongest acid.
Since pKa = – log Ka, Ka = 10–pKa
For HA: Ka = 10–3.16 = 6.9 × 10–4
For HB: Ka = 10–4.14 = 7.2 × 10–5

17.13 (a) (CH3)3N + H2O
(CH3)3NH+ + OH–

[(CH3 )3 NH + ][OH − ]
Kb =
(CH3 )3 N 
(b) SO32– + H2O
HSO3– + OH–
[HSO3− ][OH − ]
Kb =
SO32 − 
 
(c) NH2OH + H2O
NH3OH+ + OH–
[NH3OH + ][OH − ]
Kb =
[ NH 2 OH ]

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17.14 (a) HS– + H2O
H2S + OH–

[H 2S][OH − ]
Kb =
 HS− 
 
(b) H2PO4– + H2O
H3PO4 + OH–
[H3 PO4 ][OH − ]
Kb =
 H 2 PO 4− 
 
(c) HPO42– + H2O
H2PO4– + OH–
[H 2 PO 4 − ][OH − ]
Kb =
 HPO 42 − 
 
(d) HCO3– + H2O
H2CO3 + OH–
[H 2 CO3 ][OH − ]
Kb =
 HCO3− 
 
(e) HSO3– + H2O
H2SO3 + OH–
[H 2SO3 ][OH − ]
Kb =
 HSO3− 
 

17.15 For conjugate acid base pairs, Ka × Kb = Kw:

Kb = Kw ÷ Ka = 1.0 × 10–14 ÷ 2.3 × 10–11 = 4.3 × 10–4

17.16 For conjugate acid base pairs, Ka × Kb = Kw:

Ka = Kw ÷ Kb = 1.0 × 10–14 ÷ 5.5 × 10–11 = 1.8 × 10–4

17.17 HSal + H2O
H3O+ + Sal–

 H O +  Sal− 
Ka =   
3

[ HSal]
[H3O+] = 10–pH = 10–1.83 = 0.0148 M

[HSal] [H3O+] [Sal–]

I 0.200 – –
C –x +x +x
E 0.200–x +x +x

We know the [H+] is 0.0148 M

x = 0.0148
[HSal] = 0.200 – 0.0148 = 0.185 M
[Sal–] = 0.0148 M
 H O +  Sal− 
Ka = 
3   = ( 0.0148 )( 0.0148 ) = 1.2 × 10–3
[ HSal] ( 0.185 )
pKa = –log (Ka) = –log (1.18 × 10–3) = 2.93

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17.18 HBu + H2O
H3O+ + Bu–

[H3O+ ][Bu − ]
Ka =
[ HBu ]
[HBu] [H3O+] [Bu–]
I 0.01000 – –
C –x +x +x
E 0.01000–x +x +x

We know that the acid is 4.0% ionized so x = 0.01000 M × 0.040 = 0.00040 M. Therefore, our equilibrium
concentrations are [H+] = [Bu–] = 0.00040 M, and [HBu] = 0.01000 M – 0.00040 M = 0.00960 M.
Substituting these values into the mass action expression gives:
(0.00040)(0.00040)
Ka = = 1.7 × 10–5
0.00960
pKa = –log(Ka) = –log(1.7 × 10–5) = 4.78

17.19 We will use the symbol Mor and HMor+ for the base and its conjugate acid respectively:
Mor + H2O
HMor+ + OH–
[HMor + ][OH − ]
Kb =
[ Mor ]
[Mor] [HMor+] [OH–]
I 0.010 – –
C –x +x +x
E 0.010–x +x +x

At equilibrium, the pOH = 3.90.

The [OH–] = 10–pOH = 10–3.90 = 1.26 × 10–4 M = x.

Substituting these values into the mass action expression gives:

(1.26 × 10−4 )(1.26 × 10−4 )
Kb = = 1.6 × 10–6
−4
0.010 − 1.26 × 10
pKb = –log(Kb) = –log(1.61 × 10–6) = 5.79

17.20 HC6H5CO2 + H2O
H3O+ + C6H5CO2-

C H CO −   H O+ 
Ka = 
6 5 2  3  = 6.5 × 10–5
HC6 H5 CO2 

HC6H5CO2 [H3O+] C6H5CO2-

I 0.023 – –
C –x +x +x
E 0.023–x +x +x

Assume that x << 0.050 and substitute the equilibrium values into the mass action expression to get:

C H CO −   H O+ 
Ka = 
6 5 2  3  = 6.5 × 10–5
 6 5 2 
HC H CO

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Ka =
( x )( x ) = 6.5 × 10–5
( 0.023)
x = 1.2 × 10–3
[H3O+] = x = 1.2 × 10–3M
pH = –log[H3O+] = –log(1.2 × 10–3) = 2.91

17.21 C5NH4COOH + H2O
H3O+ + C5NH4COO–

[H 3O + ][C5 NH 4 COO − ]
Ka = = 1.4 × 10−5
 5
C NH 4 COOH 

[C5NH4COOH] [H3O+] [C5NH4COO–]

I 0.050 – –
C –x +x +x
E 0.050 – x +x +x

Assume that x << 0.050 and substitute the equilibrium values into the mass action expression to get:
[x][x]
Ka = = 1.4 × 10−5
[ 0.050]
Solving for x we determine that x = 8.4 × 10–4 M = [H+].
pH = –log[H+] = –log(8.4 × 10–4) = 3.08

17.22 C6H5NH2 + H2O
C6H5NH3+ + OH–

[C6 H 5 NH 3+ ][OH − ]
Kb = = 3.9 × 10−10
C6 H 5 NH 2 

[C6H5NH2] [C6H5NH3+] [OH–]

I 0.025 – –
C –x +x +x
E 0.025 – x +x +x

Assume that x << 0.025 and substitute the equilibrium values into the mass action expression to get:

Kb =
( x )( x ) = 3.9 × 10–10
( 0.025 )
x = 3.12 × 10–6
[OH–] = 3.12 × 10–6
pOH = –log[OH–] = –log(3.12 × 10–6) = 5.51

17.23 C5H5N + H2O
C5H5NH+ + OH–

[C5 H 5 NH + ][OH − ]
Kb = = 1.7 × 10 −9
C5 H 5 N 

[C5H5N] [C5H5NH+] [OH–]

I 0.010 – –
C –x +x +x
E 0.010 – x +x +x

Assume that x << 0.010 and substitute the equilibrium values into the mass action expression to get:

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[x][x]
Kb = = 1.7 × 10−9
[ 0.010]
Solving for x we determine that x = 4.1 × 10–6 M = [OH–].
pOH = –log[OH–] = –log(4.1 × 10–6) = 5.38
pH = 14.00 – pOH = 8.62

17.24 We will use the notation phenol and phenolate for the acid and its conjugate base, respectively:
phenol
H+ + phenolate
[H + ][phenolate]
Ka = = 1.3 × 10−10
[ phenol]
[phenol] [H+] [phenolate]
I 0.15 – –
C –x +x +x
E 0.15 – x +x +x

If we assume that x << 0.15, a good assumption based upon the size of Ka, we can substitute the
equilibrium values in to the mass action expression to get:
(x)(x)
Ka = = 1.3 × 10−10
0.15

Solving gives x = 4.42 × 10–6 M = [H+]

pH = –log[H+] = –log(4.42 × 10–6) = 5.35

17.25 Examine the ions in solution one at a time: The cation for acidity and the anion for basicity.
(a) NaNO2
Na+ is an ion of a Group I metal and is not acidic
NO2– is the conjugate base of HNO2, a weak acid, therefore it is a weak base.
The solution should be basic.
(b) KCl
K+ is an ion of a Group I metal and is not acidic
Cl– is the conjugate base of HCl, a strong acid, therefore it is not a strong base.
The solution should be neutral.
(c) NH4Br
NH4+ is the conjugate acid of NH3, a weak base, therefore it is a weak acid
Br– is the conjugate base of HBr, a strong acid, therefore it is not a strong base.
The solution should be acidic.

17.26 Examine the ions in solution one at a time: The cation for acidity and the anion for basicity.
(a) NaNO3
Na+ is an ion of a Group I metal and is not acidic
NO3– is the conjugate base of HNO3, a strong acid, therefore it is not a strong base.
The solution should be neutral.
(b) KOCl
K+ is an ion of a Group I metal and is not acidic
OCl– is the conjugate base of HOCl, a weak acid, therefore it is a weak base.
The solution should be basic.
(c) NH4NO3
NH4+ is the conjugate acid of NH3, a weak base, therefore it is a weak acid
NO3– is the conjugate base of HNO3, a strong acid, therefore it is not a strong base.
The solution should be acidic.

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17.27 The chloride ion is neutral since it is the conjugate base of a strong acid, HCl. The ion CH3NH3+ forms
from the reaction of CH3NH2 with water and will act as a weak acid.
CH3NH3+ + H2O
H3O+ + CH3NH2
K w 1.0 ×10−14
Ka = = = 2.3 × 10–11
Kb −4
4.4 ×10
CH3 NH 2   H3O + 
Ka =  
CH NH + 
 3 3 
The concentration of the salt, CH3NH3Cl, in water is
 1 mol CH3 NH3Cl   1 
M CH3NH3C = (25.0 g CH3NH3Cl)    = 0.740 M CH3NH3Cl
 67.53 g CH 3 NH 3 
Cl 0.500 L 
[CH3NH3+] [H3O+] [CH3NH2]
I 0.740 – –
C –x +x +x
E 0.740 – x +x +x
Assume that x is small relative to 0.740 M CH3NH3Cl.

Ka =
( x )( x ) = 2.3 × 10–11
( 0.740 )
x = 4.13 × 10–6 = [H+]
pH = –log[H+] = –log(4.13 × 10–6) = 5.39

17.28 The sodium ion is neutral since it is the salt of the strong base, NaOH. The nitrite ion is basic since it is the
salt of nitrous acid, HNO2, a weak acid. The equilibrium we are interested in for this problem is:
NO2– + H2O
HNO2 + OH–.
[HNO2 ][OH − ]
Kb =
 NO2 
−

In order to determine the value for Kb recall that Ka Kb = Kw. We can look for the value of Ka for HNO2 Kb
= 1.0 × 10–14 ÷ 4.6 × 10–4 = 2.17 × 10–11.

[NO2–] [HNO2] [OH–]

I 0.10 – –
C –x +x +x
E 0.10 – x +x +x

Assume that x << 0.10 and substitute the equilibrium values into the mass action expression to get:
[x][x]
Kb = = 2.17 × 10−11
[ ]
0.10

Solving we determine that x = 1.47 × 10–6 M = [OH–].

pOH = –log[OH–] = –log(1.2 × 10–6) = 5.83
pH = 14.00 – pOH = 8.17

17.29 Upon mixing, the NH3 will react with HBr to form NH4Br. The initial concentration of the NH4Br will be:
 0.20 mol NH 3 
mol NH3 = (500 mL solution)   = 0.10 mol NH3
 1000 mL solution 
 0.20 mol HBr 
mol HBr = (500 mL solution)   = 0.10 mol HBr
 1000 mL solution 

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The NH3 and HBr are in a 1:1 ratio, therefore the number of moles of NH4Br is 0.10. The volume of the
solution is 500 mL + 500 mL = 1000 mL = 1.0 L
The concentration of NH4Br is:
0.10 mol NH 4 Br
M NH4Br = = 0.10 M NH4Br
1.00 L solution
As previously determined, a solution of NH4Br will be acidic since NH4+ is the salt of a weak base and Br–
is the salt of a strong acid. As in the previous Practice Exercise, we need to determine the value for the
dissociation constant using the relationship Ka × Kb = Kw and the value of Kb for NH3 as listed in Table
17.3.
Ka = 1.0 × 10–14 ÷ 1.8 × 10–5 = 5.6 × 10–10. The equilibrium reaction is:
NH4+
NH3 + H+

[NH4+] [NH3] [H+]

I 0.10 – –
C –x +x +x
E 0.10 – x +x +x

Assume that x << 0.10 and substitute the equilibrium values into the mass action expression to get:
[x][x]
Ka = = 5.6 × 10 −10
[ 0.10]
Solving we determine that x = 7.5 × 10–6 M = [H+].
pH = –log[H+] = –log(7.5 × 10–6) = 5.13

17.30 NH3 is a weak base and its conjugate, the ammonium ion, is a weak acid. The cyanide ion is the conjugate
base of HCN, a weak acid. In order to determine if the solution is acidic or basic, we need to determine the
relative strength of the two components. Use the relationship Ka × Kb = Kw in order to determine the
dissociation constants for the cyanide ion and the ammonium ion.

Ka(NH4+) = Kw ÷ Kb(NH3) = 1.0 × 10–14 ÷ 1.8 × 10–5 = 5.6 × 10–10

Kb(CN–) = Kw ÷ Ka(HCN) = 1.0 × 10–14 ÷ 4.9 × 10–10 = 2.0 × 10–5

Since the Kb(CN–) is larger than the Ka(NH4+) the NH4CN solution will be basic.

17.31 Using the same logic as the previous question:

NH4+ is the salt of a weak base, and is acidic
NO2– is the salt of a weak acid, and is basic
The relative strengths of the two components must be compared.
Ka(NH4+) = Kw ÷ Kb(NH3) = 1.0 × 10–14 ÷ 1.8 × 10–5 = 5.6 × 10–10
Kb(NO2–) = Kw ÷ Ka(HNO2) = 1.0 × 10–14 ÷ 4.6 × 10–4 = 2.2 × 10–11

The Ka (NH4+) is larger than the Kb(NO2–), thus the solution will be acidic.

17.32 In the acetate buffer, there are HC2H3O2 and C2H3O2– present.
Upon addition of a strong acid, the concentration of HC2H3O2 will increase:
H+ + C2H3O2–
HC2H3O2
When a strong base is added, it reacts with the acid to form more of the acetate ion; therefore the
concentration of the acetic acid will decrease:
HC2H3O2 + OH–
C2H3O2– + H2O

17.33 (a) H+ + NH3
NH4+

(b) OH– + NH4+
H2O + NH3

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17.34 The equation is: C2H3O2– + H2O
HC2H3O2 + OH–

Start by determining Kb for acetate ion using Kw = KaKb

Kb = Kw/Ka = 1.0 × 10–14/1.8 × 10–5 = 5.56 × 10–10

HC 2 H 3O 2   OH − 
Kb =  
C H O − 
 2 3 2 

[C2H3O2–] [HC2H3O2] [OH–]

I 0.11 0.090 –
C –x +x +x
E 0.11 – x 0.090 +x +x

Kb =
[ x ][0.090 + x ]
[0.11 - x ]
assume x << 0.090 and solve for x
10
x = [OH ] = 6.79 × 10
pOH = 9.17
pH = 14.00 – 9.17 = 4.83, the difference is due to rounding errors

17.35 Find the concentrations of the acetic acid and the acetate ion:
 1 mol HC2 H3O 2  1 
M HC2H3O2 = (100.0 g HC2H3O2)    = 1.665 M
 60.053 g HC H O
2 3 2  1 L solution 
 1 mol HC 2 H3O 2   1 
M NaC2H3O2 = (100.0 g HC2H3O2)    = 1.219 M
 82.035 g HC 2 H3O 2   1 L solution 
– +
HC2H3O2
C2H3O2 + H
C H O −   H + 
Ka = 
2 3 2   = 1.8 × 10–5
HC2 H3O 2 

[HC2H3O2] [C2H3O2–] [H+]

I 1.665 1.219 –
C –x +x +x
E 1.665 – x 1.219 +x +x

Ka =
(1.219 + x )( x ) = 1.8 × 10–5
(1.665 − x )
Assume that x is small and solve for x
x = 2.5 × 10–5
pH = –log[H+] = –log(2.5 × 10–5) = 4.61

17.36 Use propanoic acid. It has a pKa of 4.89 which is within the range of pH = pKa ± 1
You may assume no volume change when adding the sodium salt of the acid to the solution.

pH = pKa + log
[salt ]
[acid ]
[acid] = 0.200 M

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5.25 = 4.89 + log

[salt ]
[0.200]
[salt] = 0.458 M
 0.458 mol NaC3 H5 O 2   96.06 g NaC3 H5 O 2 
g salt = ( 0.5000 L )    = 22.0 g NaC3H5O2
 1L   1 mol NaC3 H5 O2 
Propanoic acid buffer, 22.1 g NaC3H5O2

Using the same calculations, the following buffers can also be used:
Acetic acid buffer, 26.2 g NaC2H3O2
Hydrazoic acid buffer, 29.0 NaN3,
Butanoic acid buffer, 29.6 g NaC4H7O2,

17.37 Yes, formic acid and sodium formate would make a good buffer solution since pKa = 3.74 and the desired
pH is within one pH unit of this value.

Desired [H+] = 10-3.90 = 1.259 x 10-4 M

( mol HCHO2 )initial
Using Equation 17.10;  H +  = K a ×
 
( mol CHO )2
−
initial
Rearranging and substituting the known values we get;

H+ 
1.259 × 10−4
=   =
mol HCHO 2initial
= 0.70 mol
mol CHO 2 −initial Ka 1.8 × 10−4

0.1 mol HCHO = 0.70 x ( mol CHO2-)

mol CHO2- = 0.1 mol HCHO/0.70 = 0.1428 mol CHO2-

(0.1428 mol NaCHO2)(68.007 g/1 mol) = 9.7 g NaCHO2.

17.38 The NaOH added to a buffer solution will react with the HC2H3O2.
NaOH + HC2H3O2
NaC2H3O2 + H2O
First, calculate the amount of acid and base after the addition of the NaOH:
mol NaC2H3O2 = 1.00 mol NaC2H3O2 + 0.15 mol NaC2H3O2 = 1.15 mol NaC2H3O2
mol HC2H3O2 = 1.00 mol HC2H3O2 – 0.15 mol NaC2H3O2 = 0.85 mol HC2H3O2
1.15 mol NaC 2 H 3O 2
M NaC2H3O2 =
1 L solution
0.85 mol HC2 H 3O 2
M HC2H3O2 =
1 L solution

pH = pKa + log
[ salt ]
= 4.74 + log
(1.15) = 4.87
[acid ] ( 0.85)
The pH of the initial solution was 4.74 since the concentration of the acid equals the concentration of the
salt.
The pH change:
4.74 – 4.87 = 0.13 pH units

17.39 Calculate the moles of the salt and the acid, then calculate the pH of the solution.
 1 mol NH3 
mol NH3 = (50.0 g NH3)   = 2.94 mol NH3
 17.03 g NH3 

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 1 mol NH 4 Cl 
mol NH4Cl = (50.0 g NH4Cl)   = 0.935 mol NH4Cl
 53.49 g NH 4 Cl 
NH4+
NH3 + H+
K 1.0 ×10−14
Ka = w = = 5.6 × 10–10
Kb −5
1.8 ×10
pKa = –log(Ka) = –log(5.6 × 10–10) = 9.26

pH = pKa + log
[salt ] = 9.26 + log ( 2.94 ) = 9.76
[acid ] ( 0.935)
If 5.00 g of HCl is add, the solution will become more acidic:
NH3 + H+
NH4+
 1 mol HCl 
mol HCl = (5.00 g HCl)   = 0.137 mol HCl
 36.46 g HCl 
The number of moles of NH4+ will increase by this amount and the number of moles of NH3 will decrease
by this amount.
mol NH3 = 2.94 mol NH3 – 0.137 mol = 2.80 mol NH3
mol NH4+ = 0.935 mol + 0.137 mol = 1.07 mol NH4+

pH = pKa + log
[salt ] = 9.26 + log ( 2.80 ) = 9.67
[acid ] (1.07 )

 H O+   H PO − 
Ka =   2 4 
+ –
3
17.40 H3PO4 + H2O
H3O + H2PO4
H3 PO4 
 H O +   HPO 2− 
H2PO4– + H2O
H3O+ + HPO42– Ka =  
3 4 

 H PO − 
 2 4 
 H O +   PO 3− 
Ka =   4 
2– + 3–
3
HPO4 + H2O
H3O + PO4
 HPO 2 − 
 4 

17.41 [H+] is determined by the first protic equilibrium:

H2C6H6O6
H+ + HC6H6O6–

The mass action expression is: Ka1 = 8.0 × 10–5 = x2/0.10

x = [H+] = 2.8 × 10–3 M
pH = –log(2.8 × 10–3) = 2.55

The concentration of the anion, [HC6H6O6–], is given almost entirely by the second ionization equilibrium:
HC6H6O6–
H+ + C6H6O62– for which the mass action expression is:

 H +   C H O 2− 
=  
6 6 6 
K a2 = 1.6 × 10−12
 HC H O − 
 6 6 6 

We have used the value for Ka2 from Table 17.4. Using the value of x from the first step above gives:

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 Chapter 17

1.6 × 10 −12
=
( 2.8 × 10 ) C H O
−3
6 6 6
2− 

( 2.8 × 10 ) −3

[HC6H6O6–] = 1.6 × 10–12

17.42 CO32–(aq) + H2O
HCO3–(aq) + OH–(aq)

Kw 1.0 × 10−14
Kb = = = 2.1 × 10–4
Ka2 −11
4.7 × 10
 HCO −  OH − 
Kb = 2.1 × 10–4 = 
3  
CO 2 −
 3 

[CO32–] [HCO3–] [OH–]

I 0.10 – –
C –x +x +x
E 0.10–x +x +x

Kb = 2.1 × 10–4 =
( x )( x )
( 0.10 − x )
x = [OH–] = 4.5 × 10–3 M
pOH = –log(4.5 × 10–3) = 2.35
pH = 14.00 – 2.35 = 11.66
It is basic, but it is too basic to be a substitute for NaHCO3.

17.43 The equilibrium we are interested in for this problem is:

SO32–(aq) + H2O
HSO3–(aq) + OH–(aq)

Kb = Kw/Ka2 = 1.0 × 10–14 / 6.4 × 10–8 = 1.6 × 10–7

 HSO −  OH − 
= 
−7 3  
K b = 1.6 × 10
SO 2− 
 3 

[SO32–] [HSO3–] [OH–]

I 0.20 – –
C –x +x +x
E 0.20–x +x +x
Substituting these values into the mass action expression gives:
(x)(x)
K b = 1.6 × 10 −7 =
0.20 − x
Assume that x << 0.20 and solving gives x = 1.8 × 10–4.
x = [OH–] = 1.8 × 10–4 M
pOH = –log(1.8 × 10–4) = 3.75
pH = 14.00 – pOH = 14.00 – 3.75 = 10.25

17.44 For weak polyprotic acids, the concentration of the polyvalent ions is equal to the volume of Kan where n is
the valency. By analogy, the concentration of H2SO3 in 0.010 M Na2SO3 will be equal to Kb2 for SO32–.

17.45 (a) H2O, K+, HC2H3O2, H+, C2H3O2–, and OH–

[H2O] > [K+] > [C2H3O2–] > [OH–] > [HC2H3O2] > [H+]
(b) H2O, HC2H3O2, H+, C2H3O2–, and OH–

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 Chapter 17

[H2O] > [HC2H3O2] > [H+] = [C2H3O2–] > [OH–]

(c) H2O, K+, HC2H3O2, H+, C2H3O2–, and OH–
[H2O] > [K+] > [OH–] > [C2H3O2–]> [HC2H3O2] > [H+]
(d) H2O, K+, HC2H3O2, H+, C2H3O2–, and OH–
[H2O] > [HC2H3O2] > [K+] > [C2H3O2–]> [OH–] > [H+]

17.46 HCHO2 + H2O
H3O+ + CHO2–

[H3O + ][CHO 2 ]
Ka = = 1.8 × 10−4
[HCHO 2 ]

(a)
[HCHO2] [H3O+] [CHO2–]
I 0.100 – –
C –x +x +x
E 0.100–x +x +x

Assume x << 0.100. Solving we get x = [H3O+] = 4.2 × 10–3. The pH is 2.37.

(b) [HCHO2] = [CHO2–] so [H3O+] = Ka = 1.8 × 10–4 and the pH = 3.74.

 0.100 mol  −3
(c) mol base added = (15.0 mL)   = 1.50 × 10
 1000 mL 
 0.10 mol  −3
mol acid initially present = (20.0 mL)   = 2.00 × 10
 1000 mL 
excess acid = 2.00 × 10 −3 − 1.50 × 10−3 = 0.50 × 10 −3 moles acid
0.50 × 10−3 moles
[acid] = = 1.43 × 10−2 M
 1L 
(35 mL)  
 1000 mL 
1.50 × 10 −3 moles
[base] = = 4.29 × 10−2 M
 1L 
(35 mL)  
 1000 mL 
Substituting into the equilibrium expression and solving we get [H3O+] = 6.00 × 10–5
and the pH = 4.22.

(d) We now have a solution of formate ion with a concentration of 0.0500 M. We need Kb for formate
ion: Kb = Kw/Ka = 5.6 × 10–11. If we set up the equilibrium problem and solve we get: [OH–] =
1.7 × 10–6.
The pOH = 5.78 and the pH = 8.22.
 0.15 mol  −3
17.47 mol base added = (30.0 mL)   = 4.50 × 10
 1000 mL 
 0.20 mol  −2
mol acid initially present = (50.0 mL)   = 1.00 × 10
 1000 mL 
excess acid = (1.00 × 10–3) – (4.50 × 10–3) = 5.50 × 10–3 mol acid

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 Chapter 17

5.50 × 10 −3 moles
[acid] = = 6.88 × 10−2 M
 1L 
(80 mL)  
 1000 mL 
4.50 × 10−3 moles
[base] = = 5.63 × 10−2 M
 1L 
(80 mL)  
 1000 mL 
HCHO2 + H2O
H3O+ + CHO2–

[H3O + ][CHO 2 ]
Ka =
[HCHO 2 ]
[HCHO2] [H3O+] [CHO2–]
I 6.88 × 10–2 – 5.63 × 10–2
C –x +x +x
E 6.88 × 10–2–x +x 5.63 × 10–2+x

Assume x << 5.63 × 10–2

[x][5.63 × 10−2 ]
Ka = = 1.8 x 10−4
−2
[6.88 × 10 ]
x = 2.20 × 10−4 = [H3O + ]
pH = 3.66

Review Questions

17.1 H2O + H2O
H3O+ + OH–

Kw = [H3O+][OH–]

17.2 (a) neutral solution [H3O+] = [OH–] = 1.0 × 10–7 M

acidic solution [H3O+] > [OH–]
basic solution [H3O+] < [OH–]

(b) neutral solution pH = 7.00 pOH = 7.00

acidic solution pH < 7.00 pOH > 7.00
basic solution pH > 7.00 pOH < 7.00

17.3 pH + pOH = 14.00

17.4 The product of H+ and OH– is a constant, 1 × 10–14. By adding an acid to water the acid provides the H+
ions, this forces the water to decrease the amount of OH– in solution, thus suppressing the ionization of the
water. The same effect occurs with the OH–, but it is the base that is forcing the water to not ionize.

17.5 The leveling effect of water is a result of the strength of water as an acid or a base. If it is the weaker acid
or base in solution, then the other substance will ionize completely.

17.6 HI, HBr, HClO4, HCl, H2SO4(first dissociation), HNO3, HClO3

17.7 The reaction of the acid with a solvent, usually water, that causes the dissociation of a proton.

17.8 Strong bases are those that ionize 100 % producing an excess of OH- in solution.

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 Chapter 17

17.9 The key to a safe antacid is solubility. If the base releases OH- ions readily in water then damage to the
esophagus will occur. A low soluble base such as Mg(OH)2 will dissolve in the stomach, not in the
esophagus, and thus be safe for consumption.

17.10 HA + H2O
H3O+ + A–

[H3O+ ][A- ]
Ka =
[HA]

17.11 (a) HNO2
H+ + NO2–

(b) H3PO4
H+ + H2PO4–
(c) HAsO42–
H+ + AsO43–
(d) (CH3)3NH+
H+ + (CH3)3N

 H +   NO −   H +   H PO − 
 2   2 4 
17.12 (a) Ka =   (b) Ka =  
[ HNO2 ] H3 PO 4 
 H +   AsO 3−   H +  (CH ) N 
 4   3 3 
(c) Ka =   (d) Ka =  
 HAsO4 
2−
 (CH ) NH + 
 3 3 
17.13 B + H2O
HB+ + OH–
[HB+ ][OH ]
Kb =
[B]

17.14 (a) (CH3)3N + H2O
(CH3)3NH+ + OH–

(b) AsO43– + H2O
HAsO42– + OH–
(c) NO2– + H2O
HNO2 + OH–
(d) (CH3)2N2H2 + H2O
(CH3)2N2H3+ + OH–

(CH ) NH +   OH −   HAsO 4 2−  OH − 

Kb =     
3 3
17.15 (a) (b) Kb =
(CH3 )3 N   AsO 43− 

[ HNO2 ] OH −   (CH ) N H +   OH − 

Kb = 
3 2 2 3  
(c) Ka = (d)
 NO 2   3 2 2 2 
−
(CH ) N H

17.16 In general, there is an inverse relationship between the strength of an acid and its conjugate base; the
stronger the acid, the weaker its conjugate base. Since HCN has the larger value for pKa, we know that it is
a weaker acid than HF. Accordingly, CN– is a stronger base than F–.

17.17 (a) (b)

CH3

H2
H 3C C N H
N H

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 Chapter 17

(c)
H

H O N H

17.18 (a) (b)

CH3

H 3C N
NH 2
CH3

(c)
H H

H N N H

17.19 Percentage ionization is the number of moles ionized per liter of solution divided by the moles available per
liter of solution times 100.
moles ionized per liter
Percentage ionization = × 100%
moles available per liter

17.20 If [HA]initial < 400 × Ka or if the % ionization ≥ 5%, the initial concentration of the acid is not equal to the
equilibrium concentration. The same argument holds true for bases.

17.21 Simplification works when [HA]initial ≥ 400 × Ka

(a) 400 × (1.8 × 10–5) = 0.0072
0.0072 M < 0.020 M Use initial concentration

(b) 400 × (4.4 × 10–4) = 0.176

0.176 M > 0.10 M May not use initial concentration

(c) 400 × (1.7 × 10–6) = 6.8 × 10–4

6.8 × 10–4 M < 0.002 M Use initial concentration

(d) 400 × (1.8 × 10–4) = 7.2 × 10–2

7.2 × 10–2 M > 0.050 M May not use initial concentration

17.22 The acetylsalicylate ion is the anion of the salt of a weak acid and is therefore a weak base. The solution of
the sodium salt will be basic since the sodium ion is neutral.

17.23 The oxalate ion hydrolyzes in water, to give a basic solution, according to the equation:
C2O42– + H2O
HC2O4– + OH–

17.24 Recall that the salt of a weak acid is basic, the cation of a salt of a weak base is acidic and the salt of a
strong acid or base is neutral.

(a) acidic: NH4Br: NH4+ is the salt of NH3, a weak base.

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 Chapter 17

(b) basic: KF: F– is the anion of a salt of HF, a weak acid.

KCN: CN– is the anion of a salt of HCN, a weak acid.
KC2H3O2: C2H3O2– is the anion of a salt of HC2H3O2, a weak acid.

(c) neutral: NaI: This is a salt of a strong acid, HI, and a strong base, NaOH.
CsNO3: Metal ions with small charges are neutral and NO3– is the anion of a salt of
HNO3, a strong acid.
KBr: This is the salt of a strong acid, HBr, and a strong base, KOH.

17.25 The litmus paper will turn red indicating the presence of an acid. In section 16.4 it was stated that small,
highly charged cations are acidic in water because the water molecules that surround the metal ion easily
lose H+ ions. Al3+ was a specific example.

17.26 Kb for hydrazine is larger than Ka for acetic acid since the solution is acidic. The hydrazine reacts with
water to form a weak acid. Since the solution is acidic, the more of the hydrazine has dissociated than the
acetate ion has reacted, this occurs if Kb is larger than Ka.

17.27 Mg(OH)2 + 2NH4+
Mg2+ + 2NH3 + 2H2O

17.28 (a) H2CO3 + OH–
H2O + HCO3–

H+ + HCO3–
H2CO3

(b) H2PO4– + OH–
H2O + HPO42–

H+ + HPO42–
H2PO4–

(c) NH4+ + OH–
H2O + NH3

H+ + NH3
NH4+

(d) C6H5OH + OH–
H2O + C6H5O–

C6H5O– + H+
C6H5OH

17.29 HPO42– + H+
H2PO4 –

HPO42– + OH–
H2O + PO43–

17.30 H2SO3
HSO3– + H+ HSO3–
SO32– + H+

 HSO −   H +  SO 2−   H + 
= 
3   = 
3  
Ka 1 Ka 2
H 2SO3   HSO − 
 3 

17.31 H3C6H5O7 + H2O
H3O+ + H2C6H5O7–

 H O+  H C H O 
K a1 = 
3  2 6 5 7 
H3C6 H5 O7 

H2C6H5O7– + H2O
H3O+ + HC6H5O72–

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 Chapter 17

 H O+   HC H O 2– 
=  6 5 7 
3
Ka2
H C H O – 
 2 6 5 7 

HC6H5O72– + H2O
H3O+ + C6H5O73–

 H O+  C H O 3 
=   6 5 7 
3
Ka3
 HC H O 2 
 6 5 7 

17.32 Nearly all of the H+ in solution comes from the first ionization. The concentration of the conjugate base of
a weak polyprotic acid once deprotonated is approximately equal to the value of the equilibrium constant.
These approximations are usually valid because the value of the first ionization constant is much larger
than the second ionization constant. If the two ionization constants are not very different, the
approximation stated above will fail.

17.33 (a) SO32– + H2O
HSO3– + OH–

HSO3– + H2O
H2SO3 + OH–
(b) PO43– + H2O
HPO42– + OH–
HPO42– + H2O
H2PO4– + OH–
H2PO4– + H2O
H3PO4 + OH–
(c) C4H4O62– + H2O
HC4H4O6– + OH–
HC4H4O6– + H2O
H2C4H4O6 + OH–

17.34 Simplifying assumptions are essentially the same for polyprotic acids (see 17.32 above), and all of the
hydroxide ion comes from the first hydrolysis. The assumptions are valid because the first dissociation
constant is so much larger than the second.

17.35 The equivalence point is when the moles of acid exactly equal the moles of base. The end point is a
measured value that approximates the equivalence point.

17.36 At the equivalence point, the titrated formic acid solution will be basic.

17.37 At the equivalence point, the titrated hydrazine solution will be acidic.

17.38 An acid-base indicator is a weak acid that changes color when it is converted from its acidic form to its
basic form. Because indicators are weak acids, they will react with the titrant. Consequently, small
amounts of indicator are used so the results will not be impaired excessively by the indicator.

17.39 At the equivalence point, all of the acetic acid will have been converted to acetate ions. Since this would be
a solution of a weak base having a pH > 7, it would be argued that the use of methyl orange would be
inappropriate since the color change occurs in the range pH = 3.2 to pH = 4.4.

A better indicator for this titration would be thymol blue, or phenolphthalein which change in the pH range
of 8-10.

Review Problems

17.40 D2O
D+ + OD–, Kw = [D+] × [OD–] = 8.9 × 10–16

Since [D+] = [OD–], we can rewrite the above expression to give:

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 Chapter 17

8.9 × 10–16 = ([D+])2, [D+] = 3.0 × 10–8 M = [OD–]

pD = –log[D+] = –log(3.0 × 10–8) = 7.52
pOD = –log[OD–] = –log(3.0 × 10–8) = 7.52
pKw = pD + pOD = 15.04

17.41 It should be stated from the outset that water at this temperature is neutral by definition, since [H+] = [OH–].
In other words, the self–ionization of water still occurs on a one–to–one mole basis:
H2O
H+ + OH–.
Kw = 2.5 × 10–14 = [H+] × [OH–]
Since [H ] = [OH–], we can rewrite the above relationship:
+

2.5 × 10–14 = ([H+])2,

∴ [H+] = [OH–] = 1.6 × 10–7 M
pH = –log[H+] = –log(1.6 × 10–7) = 6.80
pOH = –log[OH–] = –log(1.5 × 10–7) = 6.80
pKw = pH + pOH = 6.80 + 6.80 = 13.60

Alternatively, for the last calculation we can write:

pKw = –log(Kw) = –log(2.5 × 10–14) = 13.60
Water is neutral at this temperature because the concentration of the hydrogen ion is the same as the
concentration of the hydroxide ion.

17.42 At 25 °C, Kw = 1.0 × 10–14 = [H+] × [OH–]. Let x = [H+], for each of the following:

(a) x(0.0085) = 1.0 × 10–14

[H+] = (1.0 × 10–14) ÷ (0.0085) = 1.2 × 10−12
pH = –log[H+] = –log(1.2 × 10−12) = 11.93
pOH = 14 – pH = 14 – 11.93 = 2.07
(b) x(5.3 × 10–5) = 1.0 × 10–14
[H+] = (1.0 × 10–14) ÷ (6.4 × 10–5) = 1.9 × 10–10 M
pH = –log[H+] = –log(1.9 × 10–10) = 9.72
pOH = 14 – pH = 14 – 9.72 = 4.28
(c) x(2.6 × 10–8) = 1.0 × 10–14
[H+] = (1.0 × 10–14) ÷ (2.6 × 10–8) = 3.8 × 10–7 M
pH = –log[H+] = –log(3.8 × 10–7) = 6.41
pOH = 14 – pH = 14 – 6.41 = 7.59
(d) x(7.8 × 10–12) = 1.0 × 10–14
[H+] = (1.0 × 10–14) ÷ (8.2 × 10–12) = 1.3 × 10–3 M
pH = –log[H+] = –log(1.3 × 10–3) = 2.89
pOH = 14 – pH = 14 – 2.89 = 11.11

17.43 At 25 °C, Kw = 1.0 × 10–14 = [H+] × [OH–]. Let x = [OH–], for each of the following:

(a) (3.5 × 10–7)x = 1.0 × 10–14

[OH–] = (1.0 × 10–14) ÷ (3.5 × 10–7) = 2.9 × 10–8 M
pH = –log[H+] = –log(3.5 × 10–7) = 6.46
pOH = 14 – pH = 14 – 6.46 = 7.54
(b) (0.0017)x = 1.0 × 10–14
[OH–] = (1.0 × 10–14) ÷ (0.0017) = 5.9 × 10–12 M
pH = –log[H+] = –log(0.0017) = 2.77
pOH = 14 – pH = 14 – 2.77 = 11.23
(c) (2.5 × 10–11)x = 1.0 × 10–14
[OH–] = (1.0 × 10–14) ÷ (2.5 × 10–11) = 4.0 × 10–4 M
pH = –log[H+] = –log(2.5 × 10–11) = 10.60
pOH = 14 – pH = 14 – 10.60 = 3.40

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 Chapter 17

(d) (7.9 × 10–2)x = 1.0 × 10–14

[OH–] = (1.0 × 10–14) ÷ (7.9 × 10–2) = 1.3 × 10–13 M
pH = –log[H+] = –log(7.9 × 10–2) = 1.10
pOH = 14 – pH = 14 – 1.10 = 12.90

17.44 pH = –log[H+] = –log(1.9 × 10–5) = 4.72

17.45 pH = –log[H+] = –log(1.4 × 10–5) = 4.85

17.46 [H+] = 10–pH and [OH–] = 10–pOH

At 25 °C, pH + pOH = 14.00

(a) [H+] = 10–pH = 10–7.96 = 1.1 × 10–8 M

pOH = 14.00 – pH = 14.00 – 7.96 = 6.04
[OH–] = 10–pOH = 10–6.04 = 9.1 × 10–7

(b) [H+] = 10–pH = 10–2.35 = 4.5 × 10–3 M

pOH = 14.00 – pH = 14.00 – 2.35 = 11.65
[OH–] = 10–pOH = 10–11.65 = 2.2 × 10–12 M

(c) [H+] = 10–pH = 10–10.85 = 1.4 × 10–11 M

pOH = 14.00 – pH = 14.00 – 10.85 = 3.15
[OH–] = 10–pOH = 10–3.15 = 7.1 × 10–4 M

(d) [H+] = 10–pH = 10–13.75 = 1.8 × 10–14 M

pOH = 14.00 – pH = 14.00 – 13.75 = 0.25
[OH–] = 10–pOH = 10–0.25 = 5.6 × 10–1 M

(e) [H+] = 10–pH = 10–6.25 = 5.6 × 10–7 M

pOH = 14.00 – pH = 14.00 – 6.25 = 7.75
[OH–] = 10–pOH = 10–7.75 = 1.8 × 10–8 M

17.47 (a) [OH–] = 10–pOH = 10–12.75 = 1.8 × 10–13 M

pH = 14.00 – pOH = 14.00 – 12.75 = 1.25
[H+] = 10–pH = 10–1.25 = 5.6 × 10–2 M

(b) [OH–] = 10–pOH = 10–6.56 = 2.8 × 10–7 M

pH = 14.00 – pOH = 14.00 – 6.56 = 7.44
[H+] = 10–pH = 10–7.44 = 3.6 × 10–8 M

(c) [OH–] = 10–pOH = 10–11.45 = 3.5 × 10–12 M

pH = 14.00 – pOH = 14.00 – 11.45 = 2.55
[H+] = 10–pH = 10–2.55 = 2.8 × 10–3 M

(d) [OH–] = 10–pOH = 10–4.72 = 1.9 × 10–5 M

pH = 14.00 – pOH = 14.00 – 4.72 = 9.28
[H+] = 10–pH = 10–9.28 = 5.2 × 10–10 M

(e) [OH–] = 10–pOH = 10–3.05 = 8.9 × 10–4 M

pH = 14.00 – pOH = 14.00 – 3.05 = 10.95
[H+] = 10–pH = 10–10.95 = 1.1 × 10–11 M

17.48 [H+] = 10–pH = 10–5.7 = 2 × 10–6 M

pOH = 14.00 – pH = 14.00 – 5.7 = 8.3
[OH–] = 10–pOH = 10–8.3 = 5 × 10–9 M

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 Chapter 17

17.49 [H+] = 10–pH = 10–3.16 = 6.92 × 10–4 M

If the concentration of H+ is doubled:
[H+] = 1.38 × 10–3 M
pH = –log[H+] = –log(1.38 × 10–3) = 2.86

17.50 HNO3 is a strong acid so [H+] = [HNO3] = 0.0035 M

pH = –log[H+] = –log(0.0035) = 2.46
pOH = 14.00 – pH = 14.00 – 2.46 = 11.54
[OH–] = 10–pOH = 10–11.54 = 2.9 × 10–12 M

17.51 HClO4 is a strong acid so [H+] = [HClO4] = 0.045 M

pH = –log[H+] = –log(0.045) = 1.35
pOH = 14.00 – pH = 14.00 – 1.35 = 12.65
[OH–] = 10–pOH = 10–12.65 = 2.24 × 10–13 M

If the concentration of H+ is doubled:

[H+] = 0.045 M × 2 = 0.090 M
pH = –log[H+] = –log(0.090) = 1.05
The pH drops by 0.3 pH units.

17.52
moles OH −  5.0 g NaOH   1 mole NaOH   1 mole OH − 
M OH − = =  
L solution  1.00 L solution   40.0 g NaOH   1 mole NaOH 
= 0.125 M OH −

pOH = –log[OH–] = –log(0.125) = 0.903

pH = 14.00 – pOH = 14.00 – 0.903 = 13.10
[H+] = 10–pH = 10–13.10 = 8.0 × 10–14 M

moles OH −
M OH − =
L solution
 0.837 g Ba(OH) 2   1 mole Ba(OH)2   2 mole OH − 
17.53 =     

 0.100 L solution   171.3 g Ba(OH)2   1 mole Ba(OH)2 
= 0.0977 M OH −

pOH = –log[OH–] = –log(9.77 × 10–2) = 1.01

pH = 14.00 – pOH = 14.00 – 1.01 = 12.99
[H+] = 10–pH = 10–12.99 = 1.02 × 10–13 M

17.54 pOH = 14.00 – pH = 14.00 – 11.40 = 2.60

[OH–] = 10–pOH = 10–2.60 = 2.5 × 10–3 M
 2.5 × 10−3 mol OH −   1 mol Ca(OH)2 
[ Ca(OH)2 ] =  1 L solution 
  2 mol OH − 
 
= 1.3 × 10 −3 M Ca(OH)2

pH = 10.40
pOH = 14 – 10.40 = 3.60
[OH–] = 10–pOH = 10–3.60 = 2.5 × 10–4 M

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 Chapter 17

 2.5 × 10 −4 mol OH −   1 mol Ca(OH) 2 

[ Ca(OH)2 ] =  1 L solution

  2 mol OH − 
 
= 1.3 × 10 −4 M Ca(OH)2

17.55 [H+] = 10–pH = 10–2.25 = 5.6 × 10–3 M

 5.6 × 10−3 mol H +   1 mol HCl   36.46 g HCl 
g HCl = ( 0.250 L )  
 1 L solution   1 mol H +   1 mol HCl 
 
= 5.1 × 10−2 g HCl

pH = 2.25 × 2 = 4.50
[H+] = 10–pH = 10–4.50 = 3.2 × 10–5 M
 3.2 × 10−5 mol H +   1 mol HCl   36.46 g HCl 
g HCl = ( 0.250 L )  
 1 L solution   1 mol H +   1 mol HCl 
 
= 2.9 × 10−4 g HCl

17.56 Since NaOH is a strong base, [NaOH] = [OH–] = 0.0020 M OH–. (Next, we make the simplifying
assumption that the amount of hydroxide ion formed from the dissociation of water is so small that we can
neglect it in calculating pOH for the solution.)

[H+] = 1 × 10–14 ÷ 0.0020 = 5.0 × 10–12 M H+

The only source of H+ is the autoionization of water. Therefore, the molarity of OH– from the ionization
water is 5.0 × 10–12 M.

17.57 The H+ concentration from the ionization of water also gives the same OH– concentration. Since the only
source of OH– is the water, the concentration of OH– is 3.4 × 10–11 M.
The total H+ concentration can be determined from:
1 × 10–14 = [H+] × [OH–] = [H+] × (3.4 × 10–11)
[H+] = 2.9 × 10–4 M H+

17.58 First calculate the molarity of OH- produced from the Ba(OH)2.

 1mol Ba(OH)2   2mol OH −   1 

2.64 x10−6 g Ba(OH)2    
−8
  = 3.08 x 10 M
 171.3 g   mol Ba(OH)2   1L 

pOH = -log(3.08 x 10-8) = 7.51

pH = 14 – 7.51 = 6.49

Notice the pH calculated from the Ba(OH)2 is less than 7. We would expect the solution to be basic but
since the amount of base added to water is so small, the salt is not the major contributor to the pH of the
solution. Thus, we cannot neglect the ionization of water in this case, since water’s ionization is a
significant contributor to the H+ and OH- concentrations in the solution.
The problem is more complicated than when acid or base concentrations are larger than 10-7M.

Let’s analyze all of the reactions:

Ba(OH)2 → Ba2+ + 2OH- complete ionization of a strong base

2H2O
H3O+ + OH- Kw = [H3O+][OH-] = 1.00 x 10-14

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 Chapter 17

We know that the concentration of cations must equal the concentration of anions for the solution to be
neutral. Therefore,

[H3O+] + 2[Ba2+] = [OH-] Charge balance equation. Remember, the Ba2+ ion’s total charge is
twice its concentration.

We also know that [OH-] = Kw/[H3O+]. Thus,

[H3O+] + 2[Ba2+] = Kw/[H3O+]

[H3O+]2 + 2[Ba2+][H3O+] – Kw = 0

[Ba2+] = (1/2)[OH-] = (1/2) 3.08 x 10-8 M = 1.54 x 10-8 M

[H3O+]2 + 3.08 x 10-8[H3O+] - 1.00 x 10-14 = 0

Solve using the quadratic equation.

[H3O+] = 8.58 x 10-8

pH = 7.07 A basic solution, though just barely!

17.59 The total [H+] is from the HCl and from the dissociation of H2O. Since HCl is a strong acid, it will
contribute 3.0 × 10–7 mol of H+ per liter of solution. We need to use the equilibrium expression to
determine the amount of H+ contributed by the water.
Kw = [H+][OH–] = (3.0 × 10–7 + x)(x) = 1.0 × 10–14
2 –7 –14
x + 3.0 × 10 x – 1.0 × 10 = 0
2

x=
−3.0 × 10−7 ± (3.0 ×10 )
−7
(
− 4 (1) −1.0 × 10−14 )
2 (1)
x = 3.03 × 10–8
Solving a quadratic equation we see that x = 3.03 × 10–8 = [OH–] = [H+] from water dissociation.
So, [H+]total = 3.0 × 10–7 + 3.03 × 10–8 = 3.30 × 10–7 and pH = 6.48.

17.60 [H+] = 10–pH = 10–2.37 = 4.27 × 10–3 M

4.27 × 10−3
% ionization = × 100% = 0.43%
1.0

17.61 NH3 + H2O
NH4+ + OH–

[H3O+] = 10–11.32 = 4.79 x 10–12

[OH–] = 1.0 x 10-14/4.79 x 10-12 = 2.09 x 10-3 = [NH4+]

moles ionized per liter

Percentage ionization = × 100%
moles available per liter
 2.09 x 10−3 
Percentage ionization = 
 0.250 
x100 = 0.84 %
 

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 Chapter 17

17.62 At 25 °C, Ka × Kb = Kw
Kb = Kw/Ka = 1.0 × 10–14 ÷ 1.8 × 10–5 = 5.6 × 10–10

17.63 At 25 °C, Ka × Kb = Kw
Ka = Kw/Kb = 1.0 × 10–14 ÷ 1.0 × 10–10 = 1.0 × 10–4

17.64 (a) At 25 °C, Ka × Kb = Kw

Kb = Kw/Ka = 1.0 × 10–14 ÷ 1.4 × 10–4 = 7.1 × 10–11

(b) Kb for acetic acid is 1.0 x 10-14/1.8 x 10-5 = 5.6 x 10-10. Therefore, since Kb for the lactate ion is smaller
than that for the acetate ion, the lactate ion is a weaker base.

17.65 (a) The conjugate base is IO3–

pKb = 14.00 – pKa = 14.00 – 0.77 = 13.23
Kb = 10–pKb = 10–13.23 = 5.9 × 10–14

(b) IO3– is a weaker base than an acetate anion, because its Kb value is smaller than that of an acetate
anion.

17.66 pH = 2.87 [H+] = 10–2.87 = 1.35 × 10–3 M

moles ionized per liter
Percentage ionization = × 100%
moles available per liter
1.35 × 10−3 M
Percentage ionization = × 100% = 0.54%
0.25 M
HA
H+ + A–

[HA] [H+] [A–]

I 0.25 – –
C – 1.35 × 10–3 1.35 × 10–3 1.35 × 10–3
E 0.25 1.35 × 10–3 1.35 × 10–3

 H +   A –  1.35 × 10−3  1.35 × 10−3 

     
Ka = = = 7.3 × 10–6
[ ]
HA [ ]
0.25

moles ionized per liter

17.67 Percentage ionization = × 100%
moles available per liter
Let x = moles of H+ in solution
xM
0.025% = × 100% x = 8.75 × 10–6 M
0.035 M
pH = –log[H+] = –log[8.75 × 10–6] = 5.06

HA
H+ + A–
[HA] [H+] [A–]
I 0.035 – –
C – 8.75 × 10–6 8.75 × 10–6 8.75 × 10–6
E 0.035 8.75 × 10–6 8.75 × 10–6

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 Chapter 17

 H +   A –  8.75 × 10−6  8.75 × 10−6 

     
Ka = = = 2.2 × 10–9
[ HA ] [ 0.035]
17.68 HIO4
H+ + IO4–
 H +   IO − 
 4 
Ka =  
[ HIO4 ]
[HIO4] [H+] [IO4–]
I 0.10 – –
C –x +x +x
E 0.10 – x +x +x

We know that at equilibrium [H+] = 0.038 M = x. The equilibrium concentrations of the other components
of the mixture are:
[HIO4] = 0.10 – x = 0.062 M and [IO4–] = x = 0.038 M.

Substituting the above values for equilibrium concentrations into the mass action expression gives:

(0.038)(0.038)
Ka = = 2.3 × 10−2
0.062
pKa = –log(Ka) = –log(2.3 × 10–2) = 1.64

17.69 HC2H2ClO2
H+ + C2H2ClO2–

 H +  C H ClO − 
 2 2 2 
Ka =  
[ HC2 H 2 ClO2 ]

[HC2H2ClO2] [H+] [C2H2ClO2–]

I 0.10 – –
C –x +x +x
E 0.10 – x +x +x

pH = 1.96 [H+] = 10–1.96 = 0.011 M = x

The equilibrium concentrations of the other components of the mixture are:
[HC2H2ClO2] = 0.10 – x = 0.089 M and [C2H2ClO2–] = x = 0.011 M.

Substituting the above values for equilibrium concentrations into the mass action expression gives:

(0.011)(0.011)
Ka = = 1.4 × 10−3
0.089
pKa = –log(Ka) = –log(1.4 × 10–3) = 2.87

17.70 pOH = 14.00 – pH = 14.00 – 11.87 = 2.13

[OH–] = 10–pOH = 10–2.13 = 7.41 × 10–3 M

CH3CH2NH2 + H2O
CH3CH2NH3+ + OH–

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 Chapter 17

 CH CH NH +  OH − 
3  
Kb = 
3 2

CH3CH 2 NH 2 

[CH3CH2NH2] [CH3CH2NH3+] [OH–]

I 0.10 – –
C –x +x +x
E 0.10–x +x +x

In the equilibrium analysis, the value of x is, therefore, equal to 7.41 × 10–3 M. Therefore, our equilibrium
concentrations are [CH3CH2NH3+] = [OH–] = 7.41 × 10–3 M, and [CH3CH2NH2] = 0.10 M – 7.41 × 10–3 M
= 0.0926 M.

Substituting these values into the mass action expression gives:

Kb =
( 7.41 × 10 )( 7.41 × 10 ) = 5.9 × 10
−3 −3
−4
0.0926
pKb = –log(Kb) = –log(5.9 × 10–4) = 3.23
moles ionized per liter
Percentage ionization = × 100%
moles available per liter
7.4 × 10−3
Percentage ionization = × 100% = 7.4%
0.10

17.71 HONH2 + H2O
HONH3+ + OH–

 HONH +  OH − 
3  
Kb = 
[ HONH 2 ]
pOH = 14.00 – pH = 14.00 – 10.11 = 3.89
[OH–] = 10–3.88 = 1.3 × 10–4 M

In the equilibrium analysis, the value of x is, therefore, equal to 1.3 × 10–4 M:

[HONH2] [HONH3+] [OH–]

I 0.25 – –
C –x +x +x
E 0.25 – x +x +x

Therefore, our equilibrium concentrations are

[HONH3+] = [OH–] = 1.3 × 10–4 M, and
[HONH2] = 0.15 M – 1.3 × 10–4 M = 0.15 M.

Substituting these values into the mass action expression gives:

Kb =
(1.3 × 10 )(1.3 × 10 ) = 1.1 × 10
−4 −4
−7
0.15
pKb = –log(Kb) = –log(1.1 × 10–7) = 6.96
moles ionized per liter
Percentage ionization = × 100%
moles available per liter

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 Chapter 17

1.3 × 10-4
Percentage ionization = × 100% = 0.087%
0.15

17.72 HC3H5O2 + H2O
H3O+ + C3H5O2–

[H 3O + ][C3 H 5 O 2 − ]
Ka = = 1.4 × 10 −4
HC3 H 5 O2 

[HC3H5O2] [H3O+] [C3H5O2–]

I 0.125 – –
C –x +x +x
E 0.125 – x +x +x
Assume x << 0.125
[x][x]
Ka = = 1.4 × 10−4 x = 4.2 × 10−3 = [H3O+ ]
[ 0.125]
pH = 2.38

[HC3H5O2] = 0.121 M
[H+] = 4.2 × 10–3 M
[C3H5O2–] = 4.2 × 10–3 M

17.73 H2O2
H+ + HO2–

[H + ][HO 2 − ]
Ka = = 2.4 × 10−12
[ H 2 O2 ]
[H2O2] [H+] [HO2–]
I 1.0 – –
C –x +x +x
E 1.0 – x +x +x

Substituting these values into the mass action expression gives:

(x)(x)
Ka = = 2.4 × 10 −12
1.0 − x

Assuming x << 1.0 we determine that x = 1.6 × 10–6 M = [H+]

[H+] = 1.6 × 10–6 M
[HO2–] = 1.6 × 10–6 M
[H2O2] = 1.0 M – (1.6 × 10–6 M) = 1.0 M

pH = –log[H+] = 5.80

17.74 Kb = 10–pKb = 10–5.80 = 1.58 × 10–6

Cod + H2O
HCod+ + OH–
 HCod +   OH − 
Kb =   
= 1.58 × 10−6
[ Cod ]

385
 Chapter 17

[Cod] [HCod+] [OH–]

I 0.025 – –
C –x +x +x
E 0.025 – x +x +x

Substituting these values into the mass action expression gives:

Kb =
( x )( x ) = 1.58 × 10−6
0.025 − x

If we assume that x << 0.025 we get; x2 = 3.95 × 10–8,

x = 1.99 × 10–4 M = [OH–]
pOH = –log[OH–] = –log(1.99 × 10–4) = 3.70
pH = 14.00 – pOH = 14.00 – 3.70 = 10.30

17.75 C6H5N + H2O
HC6H5N+ + OH–

Kb = 10–pKb = 10–8.77 = 1.70 × 10–9
 HC H N +   OH − 
Kb = 
6 5  
= 1.70 × 10−9
C6 H5 N 

[C6H5N] [HC6H5N+] [OH–]

I 0.25 – –
C –x +x +x
E 0.25 – x +x +x

Assume x << 0.25

Kb =
( x )( x ) = 4.25 × 10−10 x = 2.1 × 10−5 = [OH − ]
0.25
pOH = 4.69 pH = 9.31

17.76 [H+] = 10–pH = 10–2.95 = 1.1 × 10–3 M

HC2H3O2
H+ + C2H3O2–
[H + ][C 2 H 3O 2 − ]
Ka = = 1.8 × 10−5
HC 2 H3O2 

[HC2H3O2] [H+] [C2H3O2–]

I Z – –
C –x +x +x
E Z–x +x +x

Substituting these values into the mass action expression gives:

(x)(x)
Ka = = 1.8 × 10−5
Z−x

386
 Chapter 17

Assuming x << Z and knowing that x = 1.1 × 10–3 M, we can solve for Z and find Z = 0.070. The initial
concentration of HC2H3O2 is 0.070 M.

17.77 Let Z = initial concentration of NH3.

NH3 + H2O
NH4+ + OH–

 NH +  OH − 
4  
Kb =  = 1.8 × 10−5
 NH3 

[NH3] [NH4+] [OH–]

I Z – –
C –x +x +x
E Z–x +x +x

Assume x << Z
(x)(x) (x)(x)
Kb = = 1.8 × 10−5 Z =
Z 1.8 × 10−5
pOH = 14 – pH = 14 – 11.35 = 2.65
x = [OH–] = 10–pOH = 10–2.65 = 2.24 × 10–3 M
Z = 0.28 M
 0.28 mol 
mol NH3 = (500 mL)  = 0.14 mol NH3
 1000 mL 

17.78 CN– + H2O
HCN + OH–

[ HCN ] OH −
 Kw 1.0 × 10−14
Kb = = = = 2.0 × 10−5
CN  −
Ka 4.9 × 10 −10

[CN–] [HCN] [OH–]

I 0.0050 – –
C –x +x +x
E 0.0050 – x +x +x

Assume that x << 0.0050

( x )( x )
Kb = = 2.0 × 10 5 x = 3.2 × 10 4 = [OH ]
0.0050
Wait!!!! 3.2 × 10 4 is not << 0.0050
So, use the method of successive approximations.

( x )( x )
Kb = = 2.0 × 10−5 x = 3.1× 10−4
0.0050 − 0.00032
(x)(x)
Kb = = 2.0 × 10−5 x = 3.1 × 10−4
0.0050 − 0.00031

x = 3.1 × 10–4 = [OH–]

pOH = 3.51
pH = 10.49

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 Chapter 17

17.79 HA + H2O
H3O+ + A–

 H O+   A − 
Ka =     = 1.4 × 10−3
3

[ HA ]
[HA] [H3O+] [A–]
I 0.020 – –
C –x +x +x
E 0.020 –x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression and assuming
that x << 0.020 gives:

Ka =
( x )( x ) = 1.36 × 10−3 x = 5.3 × 10–3 Wait!!! 5.3 × 10-3 is not << 0.020
0.020
Use the method of successive approximations
(x)(x)
Ka = = 1.4 × 10−3 x = 4.5 × 10−3
0.020 -0.0053
(x)(x)
Ka = = 1.4 × 10−3 x = 4.6 × 10−3
0.020 − 0.0045
So, x = 4.6 × 10–3 = [H3O+]
pH = 2.34

17.80 Ka = 10–pKa = 10–4.92 = 1.2 × 10–5

H–Paba
H+ + Paba–
 H +   Paba − 
Ka =     = 1.2 × 10−5
[ H − Paba ]
[H–Paba] [H+] [Paba–]
I 0.030 – –
C –x +x +x
E 0.030 – x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression and assuming
that x << 0.030 gives:

Ka =
[ x ][ x ] = 1.2 × 10−5
[0.030]
x2 = 3.6 × 10–7, x = 6.0 × 10–4 M = [H+]
pH = –log[H+] = –log(6.0 × 10–4) = 3.22

17.81 Ka = 10–pKa = 10–4.01 = 9.8 × 10–5

H–Bar
H+ + Bar–
 H +   Bar − 
Ka =     = 9.8 × 10−5
[ H − Bar ]

388
 Chapter 17

[H–Bar] [H+] [Bar–]

I 0.020 – –
C –x +x +x
E 0.020 – x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression and assuming
that x << 0.020 gives:
( x )( x )
Ka = = 9.8 × 10−5 x = 1.4 × 10−3 Wait!!!! 1.4 × 10−3 is not << 0.020
0.020
Use method of successive approximations
(x)(x)
Ka = = 9.8 × 10−5 x = 1.4 × 10−3
0.020 -0.0014
So, x = 1.4 × 10−3 = [H3O + ]
pH = 2.85

17.82 NaCN will be basic in solution since CN– is a basic ion and Na+ is a neutral ion.
CN– + H2O
HCN + OH–
For HCN, Ka = 4.9 × 10–10, we need Kb for CN–;
Kb = Kw/Ka = (1.0 × 10–14) ÷ (4.9 × 10–10) = 2.0 × 10–5
[ HCN ] OH − 
Kb = = 2.0 × 10−5
CN 
−

[CN–] [HCN] [OH–]

I 0.25 – –
C –x +x +x
E 0.25 – x +x +x

Substituting these values into the mass action expression gives:

Kb =
( x )( x ) = 2.0 × 10−5
0.25 − x

Assuming that x << 0.25 we can solve for x and determine;

x = 2.2 × 10–3 M = [OH–]
pOH = –log[OH–] = –log(2.2 × 10–3) = 2.65
pH = 14.00 – pOH = 14.00 – 2.65 = 11.35
Concentration of HCN is equal to that of hydroxide ion: 2.2 × 10–3 M

17.83 KNO2 will be basic in solution since NO2– is a basic ion and K+ is neutral.
NO2– + H2O
HNO2 + OH–
For HNO2, Ka = 4.6 × 10–4, we need Kb for NO2–;
Kb = Kw/Ka = (1.0 × 10–14) ÷ (4.6 × 10–4) = 2.2 × 10–11
[ HNO2 ] OH − 
Kb = = 2.2 × 10−11
 NO 2− 

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 Chapter 17

[NO2–] [HNO2] [OH–]

I 0.35 – –
C –x +x +x
E 0.35–x +x +x

Substituting these values into the mass action expression gives:

Kb =
( x )( x ) = 2.2 × 10−11
0.35 − x
Assuming that x << 0.35 we can solve for x and determine the equilibrium concentrations;
x = 2.8 × 10–6 M = [OH–] = [HNO2]
pOH = –log[OH–] = –log(2.8 × 10–6) = 5.56
pH = 14.00 – pOH = 14.00 – 5.56 = 8.44

17.84 A solution of CH3NH3Cl will be acidic since the Cl– ion is neutral and the CH3NH3+ ion is acidic.
CH3NH3+
H+ + CH3NH2
For CH3NH2, Kb = 4.4 × 10–4. We need Ka for CH3NH3+;
Ka = Kw/Kb = (1.0 × 10–14) ÷ (4.4 × 10–4) = 2.3 × 10–11
 H +  CH NH 
 3 2
Ka =   = 2.3 × 10−11
CH NH + 
 3 3 

[CH3NH3+] [H+] [CH3NH2]

I 0.18 – –
C –x +x +x
E 0.18 – x +x +x

Substituting these values into the mass action expression gives:

Ka =
( x )( x ) = 2.3 × 10−11
0.18 − x

Assuming that x << 0.18 we can solve for x and determine;

x = 2.0 × 10–6 M = [H3O+]
pH = –log[H3O+] = –log(2.0 × 10–6) = 5.69

17.85 Hydrazinium chloride is the acidic salt of hydrazine N2H4.

N 2H 5+ + H 2O
H 3O + + N 2H 4
H O+  [ N H ]
Ka =   2 4
3 Kw
K b for hydrazine is 1.3 × 10−6 so K a = = 7.7 × 10−9
N H +  Kb
 2 5 

[N2H5+] [H3O+] [N2H4]

I 0.10 – –
C –x +x +x
E 0.10 – x +x +x

Assume x << 0.10

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 Chapter 17

( x )( x )
Ka = = 7.7 × 10−9 x = 2.8 × 10−5 = [H3O+ ]
0.10
pH = 4.56

17.86 Let HNic symbolize the nicotinic acid

Nic– + H2O
HNic + OH–

[ HNic] OH −

Kb =
 Nic − 

[Nic–] [HNic] [OH–]

I 0.18 – –
C –x +x +x
E 0.18 – x +x +x

Assume x << 0.18

Kb =
( x )( x )
0.18
We know x = [OH–]
pH = 9.05 and pOH = 4.95
and [OH–] = 10–pOH = 1.1 × 10–5 = x
(1.1 × 10−5 )2
Kb = = 7.0 × 10−10
0.18
1× 10 –14
Ka = = 1.4 × 10–5
7.0 × 10 –10

17.87 The reaction of the weak base in water is: B + H2O
BH+ + OH–
The salt will react as: BH+
H+ + B
 H +  [ B]
Ka =  
 BH + 
 

[BH+] [H+] [B]

I 0.15 – –
C –x +x +x
E 0.15 – x +x +x

At equilibrium, the pH = 4.28 and [H+] = 5.2 × 10–5 M = x. Substituting these values into the mass action
expression gives:

Ka =
( x )( x )
=
(5.2 × 10 )(5.2 × 10 ) = 1.8 × 10
−5 −5
−8
0.15 − x 0.15 − ( 5.2 × 10 ) −5

Recall that Ka × Kb = Kw, so Kb = Kw ÷ Ka = 1.0 × 10–14 ÷ 1.8 × 10–8 = 5.6 × 10–7

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 Chapter 17

17.88 OCl– + H2O
HOCl + OH–

[ HOCl] OH −
 Kw 1.0 × 10−14
Kb = = = = 3.3 × 10 −7
OCl  −
Ka 3.0 × 10 −8

 5.1 g NaOCl  1 mol NaOCl   1.0 g   1000 mL 

[OCl ] =     
 100 g solution  74.44 g NaOCl   1 mL   1 L 
= 0.68 M

[OCl–] [HOCl] [OH–]

I 0.68 – –
C –x +x +x
E 0.68 – x +x +x

Assume that x << 0.68

( x )( x ) 7 4
Kb = = 3.3 × 10 x = 4.7 × 10 = [OH ]
0.68
pOH = 3.33
pH = 10.67

17.89 The conjugate acid BH+ is acidic due to the following equilibrium:
BH+
H+ + B

The base Y– has the following equilibrium:

Y– + H2O
HY + OH–

If a solution of the salt BHY is basic, it can only mean that Y– is a stronger base than B:
BH+ + Y–
HY + B

This can happen only if HY is a weaker acid than BH+. We conclude that pKa for HY is greater than 5.

17.90 HC2H3O2
H+ + C2H3O2–

[H + ][C 2 H3O 2 − ]
Ka = = 1.8 × 10−5
HC 2 H3O2 

[HC2H3O2] [H+] [C2H3O2–]

I 0.14 – 0.27
C –x +x +x
E 0.14 – x +x 0.27 + x

Substituting these values into the mass action expression gives:

(x)(0.27 + x)
Ka = = 1.8 × 10 −5
0.14 − x

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 Chapter 17

Assume that x << 0.14 M and x << 0.27 M, then;

 0.27 
x ×  ≈ 1.8 × 10 −5
 0.14 
 0.14 
x ≈  × 1.8 × 10 −5
 0.27 
x ≈ 9.3 × 10–6 M = [H+]
pH = –log [H+] = 5.03

17.91 C2H3O2– + H2O
HC2H3O2 + OH–

[HC 2 H3O 2 ][OH − ] Kw 1.0 × 10−14
Kb = = = = 5.6 × 10 −10
C 2 H3O 2 −  Ka 1.8 × 10 −5

[C2H3O2–] [HC2H3O2] [OH–]

I 0.27 0.14 –
C –x +x +x
E 0.27 – x 0.14 + x +x

Substituting these values into the mass action expression gives:

(0.14 + x)(x)
Kb = = 5.6 × 10 −10
0.27 − x

Assume that x << 0.14 M and x << 0.27 M, then;

 0.14 
x ×  ≈ 5.6 × 10 −10
 0.27 
 0.27 
x ≈  × 5.6 × 10−10
 0.14 
x ≈ 1.08 × 10–9 M = [OH–]

pOH = –log [OH–] = 8.97

pH = 14.00 – pOH = 5.03

The answer is identical no matter which direction we choose to solve it.

17.92 The equilibrium we will consider in this problem is: NH3 + H2O
NH4+ + OH–
 NH +  OH − 
4  
Kb =  = 1.8 × 10 −5
 NH3 
( 0.50) OH −
 = 1.8 × 10−5
=
0.30

[OH–] = 1.1 × 10–5 M

pOH = –log[OH–] = –log(1.1 × 10–5) = 4.97
pH = 14.00 – pOH = 14.00 – 4.97 = 9.03

17.93 Now we consider the equilibrium; NH4+
H+ + NH3

We know that KaKb = Kw, so Ka = Kw/Kb = 5.6 × 10–10.
 H +  NH3 
Ka =   = 5.6 × 10−10
 NH 4 + 
 

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 Chapter 17

 H +  ( 0.30)
=   = 5.6 × 10−10
0.50
[H+] = 9.3 × 10–10 M and pH = 9.03

Notice that the two values calculated are the same.

17.94 Any H+ produced will react with NH3, reducing its concentration, to produce NH4+, thus increasing its
concentration.

H+ + NH3 → NH4+

The amount of H+ produced in 35 seconds = (1.8 x 10-6 mol s-1)(35 s) = 6.3 x 10-5 mol

The concentration of NH3 will decrease by: 6.3 x 10-5 mol/0.0025 L = 2.5 x 10-2 M and the NH4+ will
increase by the same amount.

17.95 Any H+ consumed will react with C2H3O2− , reducing its concentration, to produce HC2H3O2 thus
increasing its concentration.

H+ + C2H3O2− → HC2H3O2

The amount of H+ consumed in 3.45 minutes = (1.8 x 10-7 mol min-1)(3.45 min) = 6.21 x 10-7 mol

The concentration of C2H3O2− will decrease by: 6.21 x 10-7 mol/0.0025 L = 2.5 x 10-4 M and the HC2H3O
will increase by the same amount.

17.96 The initial pH of the buffer is 5.03 as determined in Review Problem 17.90. The added acid, 0.025 mol,
will react with the acetate ion present in the buffer solution. Assume the added acid reacts completely. For
each mole of acid added, one mole of C2H3O2– is converted to HC2H3O2. Since 0.025 mol of acid is added;

[HC2H3O2]final = (0.14 + 0.025) M = 0.165 M

[C2H3O2–]final = (0.27 – 0.025) M = 0.245 M

Now, substitute these values into the mass action expression to calculate the final [H+] in solution;
 H +  (0.245)
  = 1.8 × 10−5
(0.165)
[H+] = 1.2 × 10–5 mol L–1 and the pH = 4.92

The pH of the solution changes by 5.03 – 4.92 = –0.11 pH units upon addition of the acid.

17.97 The initial pH is 9.03 as calculated in Review Problem 17.92. For every mole of OH− added, one mol of
NH4+ will be changed to one mol of NH3. Since we added 0.20 M x 0.025 L = 0.005 mol OH−:

 NH 4 +  = (0.50 M x 0.500 L − 0.005)/0.525 L = 0.47 M

 final
 NH3 final = (0.30 M x 0.500 L + 0.005 M )/0.525 L = 0.295 M

Using these new concentrations, we can calculate a new pH:

 NH +   OH −  (0.47)  OH − 
4  
Kb =  = = 1.8 × 10−5
 NH3  0.295
[OH–] = 1.13 × 10–5 M, the pOH = 4.95 and the pH = 9.05

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 Chapter 17

As expected, when an base is added, the pH increases. In this problem, the pH increases by 0.02 pH units
from 9.03 to 9.05.

17.98 The initial pH can be calculated using the Henderson-Hasselbalch equation.

 [ HB + ] 
pOH = pKb + log  
 [ B] 
 0.20 
pOH = (4.74) + log  
 0.25 
pOH = 4.64 pH = 14.00 - 4.64 = 9.36
For every mole of H+ added, one mol of NH3 will be changed to one mol of NH4+. Since we added 6.3 x
10-5 mol H+:

 NH 4 +  6.3 x10 −5 mol

= 0.20 M + = 0.2252 M
  final 0.0025 L
6.3 x10 −5 mol
 NH3 final = 0.25 M − = 0.2248 M
0.0025 L

Using these new concentrations, we can calculate a new pH:

 NH +  OH −  (0.2252) OH − 
4  
Kb =  = = 1.8 × 10−5
 NH3  0.2248
[OH–] = 1.8 × 10–5 M, the pOH = 4.74 and the pH = 9.26

As expected, when an acid is added, the pH decreases. In this problem, the pH decreases by 0.10 pH units
from 9.36 to 9.26.

17.99 The initial pH can be calculated using the Henderson-Hasselbalch equation.

 [ A− ] 
pH = pKa + log  
 [ HA] 
 0.25 
pH = (4.74) + log  
 0.15 
pOH = 4.96 pH = 14.00 - 4.96 = 9.04

For every mole of H+ added, one mol of C2H3O2− will be changed to one mol of HC2H3O2. Since we
added 6.21 x 10-7 mol H+:

6.21x10−7 mol
 HC2 H 3O2 final = 0.15 M + = 0.1502 M
0.0025 L
C H O −  6.21x10−7 mol
= 0.25 M − = 0.2498 M
 2 3 2  final 0.0025 L

Using these new concentrations, we can calculate a new pH:

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 Chapter 17

C H O −   H+ 
 = (0.2498)  H  = 1.8 × 10−5
+

Ka = 
2 3 2 

HC2 H3O2  0.1502

[H+] = 1.1 × 10–5 M, the pH = 4.96 and the pH = 9.04

We would expected when acid is removed the pH should increase. In this problem, the amount of acid
consumed is so small that no effect on the pH can be determined.

A− 
17.100 pH = pK a + log
[anion ] = pK a + log  
[ acid ] [ HA ]
4.00 = 4.74 + log( [NaC2H3O2]/[HC2H3O2] )
–0.74 = log[NaC2H3O2]/[HC2H3O2]
[NaC2H3O2]/[HC2H3O2] = 0.18
[NaC2H3O2] = 0.18 × [HC2H3O2] = 0.18 × 0.12 = 0.0216 M
Thus to the 1 L of acetic acid solution we add: 0.0216 mol NaC2H3O2 × 82.0 g/mol = 1.8 g NaC2H3O2.

A− 
17.101 pH = pK a + log
[anion ] = pK a + log  
[ acid ] [ HA ]
3.50 = 3.74 + log([NaCHO2]/[HCHO2])
[NaCHO2]/[HCHO2] = 0.575
[NaCHO2] = 0.575 × [HCHO2] = 0.575 × 0.15 = 0.0863 M
Thus, to the 1 L of formic acid solution we add: 0.0863 mol NaCHO2 × 68.0 g/mol = 5.9 g NaCHO2,
assuming no increase in volume upon addition of the sodium formate.

17.102 The equilibrium is; HC2H3O2
H+ + C2H3O2–

[H + ][C 2 H3O 2 − ]
Ka = = 1.8 × 10−5
HC 2 H3O2 

 H +  (0.110)
The initial pH is;   = 1.8 × 10−5 , [H+] = 1.636 × 10–5 M and pH = 4.79. In this calculation
0.100
we are able to use either the molar concentration or the number of moles since the volume is constant in
this portion of the problem.

In order to calculate the change in pH, we need to determine the concentrations of HC2H3O2 and C2H3O2–
after the complete reaction of the added acid. One mole of C2H3O2– will be consumed for every mole of
acid added and one mole of HC2H3O2 will be produced. The number of moles of acid added is:
 0.100 mol HCl   1 mol H 
+
mol H + = (30.00 mL HCl)     = 3.00 × 10−3 mol H +
 1000 mL HCl  1 mol HCl 


Since the volume of the new concentrations of HC2H3O2 and C2H3O2– are:
( 0.100 mol + 0.00300 mol )
HC2 H3O 2 final = 0.130 L
= 0.792 M

C H O −  ( 0.110 mol − 0.00300 mol )

= = 0.823 M
 2 3 2  final 0.130 L

Note: The new volume has been used in these calculations.

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 Chapter 17

[H + ][C2 H3O2 − ] [H + ](0.823)

Ka = = = 1.8 × 10−5
 2 3 2 
HC H O (0.792)
[H+] = 1.73 × 10–5 M and pH = 4.76

Notice that the change in pH is very small in spite of adding a strong acid. If the same amount of HCl were
added to water, a completely different effect would be observed.

Since HCl is a strong acid, the [H+] in a water solution will be the result of the strong acid dissociation. We
do, of course, need to account for the dilution. Using the dilution equation, M1V1 = M2V2.

1L 1L
30 mL x x 0.100M = M x (125 + 30 mL) x
1000 mL 1000 mL

M = 0.0194 mol L–1 and the pH = 1.71. The change in pH in this case is 7.00 – 1.71 = 5.29 pH units. A
significantly larger change!!

17.103 The initial pH is 9.03. We want to lower the pH to 8.98, a decrease of 0.050 pH units. First we will
calculate the ratio of acid and its conjugate base:

[ cation ] = pK + log BH 

+
pOH = pK b + log a
[ base] [ B]
+
14.00–8.98 = 4.74 + log([NH4 ]/[NH3])
[NH4+]/[NH3] = 1.91
We need a final ratio of conjugate base to acid of 1.91. Initially there are 0.050 moles of ammonium ion
and 0.030 moles of ammonia. We will add a strong acid using up some of the ammonia and forming
additional ammonium. For every mole of ammonium that reacts, one mole of ammonia will be formed.
We can solve the following equation:

0.050 moles ammonium + x moles H +

= 1.91
0.030 moles ammonia – x moles H +

Solving we determine x = 2.51 × 10–3 mole H+. This is the number of moles of HCl needed to change the
pH by 0.05 pH units.

 1 mol HCl   1000 mL 

(
mL = 2.51 × 10−3 mol H +  )
 1 mol H +   0.15 mol HCl 
= 17 mL .

Thus, we need to add only 17 mL to the 100 mL of buffer.

If we added 17 mL of 0.15 M HCl directly to 100 mL of pure water, we would find the pH = 1.66. Thus,
the pH of pure water would change by 5.34 pH units as opposed to the 0.05 pH unit change in the buffer

17.104 H2C6H6O6 + H2O
H3O+ + HC6H6O6– Ka1 = 8.0 × 10 –5

HC6H6O6– + H2O
H3O+ + C6H6O62– Ka2 = 1.6 × 10–12

[H2C6H6O6] [H3O+] [HC6H6O6–]

I 0.15 – –
C –x +x +x
E 0.15 – x +x +x

Assume x << 0.15

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 Chapter 17

[x][x]
Ka = = 8.0 × 10−5 x = 3.5 × 10−3
[0.15]
[H 2 C6 H 6 O6 ] ≅ 0.15 M
[H3O + ] = [HC6 H 6 O6− ] = 3.5 × 10−3 M
The concentration of the ascorbate ion equals K a2
[C6 H 6 O6 2− ] = 1.6 × 10−12 M
pH = 2.46
pOH = 11.54
[OH–] = 2.9 × 10–12 M

17.105 As we do with most diprotic weak acids, assume that all of the H+ results from the first dissociation and all
of the divalent anion results from the second dissociation. And, since the second dissociation constant is
much smaller than the first dissociation constant, the concentration of the divalent anion is equal to the
second dissociation constant.
 H TeO −   H + 
Ka 1 = 
5 6   = 2 × 10−8
H6TeO6
H5TeO6– + H+
H 6 TeO6 
 H TeO 2 −   H + 
= 
– 2– +
4 6   = 1 × 10−11
H5TeO6
H4TeO6 + H Ka 2
 H TeO − 
 5 6 

[H6TeO6] [H5TeO6–] [H+]

I 0.25 – –
C –x +x +x
E 0.25 – x +x +x

 H TeO −   H + 
= 
5 6   = (x) (x) = 2 × 10−8
Ka 1
H 6 TeO6  (0.25 - x)

Assume that x << 0.25 then; x2 = (0.25)(2 × 10–8) and x = 7.1 × 10–5 M

[H4TeO62–] = Ka2 = 1 × 10–11 M

[H+] = 7.1 × 10–5 M
[H5TeO6–] = 7.1 × 10–5 M
pH = – log[H+] = – log(7.1 × 10–5) = 4.2

 H PO −   H O + 
= 
– +
2 4  3  = 7.5 × 10−3
17.106 H3PO4 + H2O
H2PO4 + H3O K a1
H3 PO 4 
 HPO 2−   H O + 
= 
– 2– +
4  3  = 6.2 × 10−8
H2PO4 + H2O
HPO4 + H 3O K a2
 H PO − 
 2 4 
 PO 3−   H O+ 
= 
2– 3– +
4  3  = 4.2 × 10−13
HPO4 + H2O
PO4 + H3O K a3
 HPO 2− 
 4 
The following assumptions are made:

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 Chapter 17

[H+]total ≈ [H+]first step

[H2PO4–]total ≈ [H2PO4–]first step
[HPO42–]total ≈ [HPO42–]second step

The first dissociation:

[H3PO4] [H2PO4–] [H3O+]
I 2.0 – –
C –x +x +x
E 2.0 – x +x +x

 H PO −   H O + 
= 
2 4  3  = (x)(x)
K a1 = 7.5 × 10−3
H3 PO 4  (2.0 − x)

Solve for x by successive approximations or by the quadratic equation:

x = 0.12 M = [H3O+] = [H2PO4–]
[H3PO4] = 2.0 – 0.12 = 1.9 M
pH = –log(0.12) = 0.92

The second dissociation:

[H2PO4–] [HPO42–] [H3O+]
I 0.12 – 0.12
C –x +x +x
E 0.12 – x +x 0.12 + x
Assume that x << 0.12, therefore 0.12 – x ≈ 0.12 and 0.12 + x ≈ 0.12

(x)(0.12)
K a2 = = 6.2 × 10−8
(0.12)
x = 6.2 × 10–8 = [HPO42–]

The third dissociation:

[HPO42–] [PO43–] [H3O+]
–8
I 6.3 × 10 – 0.12
C –x +x +x
E 6.3 × 10–8 – x +x 0.12 + x
Assume that x << 6.2 × 10–8, therefore 6.2 × 10–8 – x ≈ 6.2 × 10–8 and 0.12 + x ≈ 0.12
(x)(0.12)
K a3 = = 4.2 × 10 −13
(6.2 × 10−8 )

Solving for x we get, x = 2.2 × 10–19 = [PO43–]

17.107 H3AsO4 + H2O
H3O+ + H2AsO4– Ka1 = 5.5 × 10–3

H2AsO4– + H2O
H3O+ + HAsO42– Ka2 = 1.7 × 10–7
HAsO42– + H2O
H3O+ + AsO43– Ka3 = 5.1 × 10–12
[HAsO42–] = 1.7 × 10–7

The following assumptions are made:

[H+]total ≈ [H+]first step
[H2AsO4–]total ≈ [H2AsO4–]first step
[HAsO42–]total ≈ [HAsO42–]second step

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 Chapter 17

Now solve using Ka1 = 5.5 × 10–3 for the other concentrations:
[H3AsO4] [H2AsO4–] [H+]
I 0.25 – –
C –x +x +x
E 0.25 – x +x +x

 H AsO −   H + 
K a1 = 
2 4   = (x)(x)
= 5.5 × 10−3
 3
H AsO 4  ( 0.25 − x )
Solve for x by successive approximations or by the quadratic equation:
x = 0.034 M = [H+] = [H2AsO4–]
[H3AsO4] = 0.25– 0.034 = 0.216 M
pH = –log(0.034) = 1.47
[H2AsO4–] = 0.034 M

For the concentration of HAsO42–

 HAsO 2−   H + 
Ka2 = 
4   = 1.7 × 10–7
 H AsO − 
 2 4 

 HAsO 2−  ( 0.034 )
Ka2 = 
4 
= [HAsO42–] = 1.7 × 10–7
( 0.034 )

 H PO −   H O + 
= 
– +
2 3  3  = 5.0 × 10−2
17.108 H3PO3 + H2O
H2PO3 + H3O Ka 1
H3 PO3 
 HPO 2 −   H O + 
Ka 2 = 
– 2– +
3  3  = 2.0 × 10−7
H2PO3 + H2O
HPO3 + H3O
 H PO − 
 2 3 
To simplify the calculation, assume that the second dissociation does not contribute a significant amount of
H+ to the final solution. Solving the equilibrium problem for the first dissociation gives:

[H3PO3] [H2PO3–] [H3O+]

I 1.0 – –
C –x +x +x
E 1.0 – x +x +x

 H PO −   H + 
= 
2 3   = (x) (x) = 5 × 10−2
Ka 1
H3 PO3  (1.0 − x)

Because K a 1 is so large, a quadratic equation must be solved. On doing so we learn that

x = 0.20 M = [H3O+] = [H2PO3–].
pH = – log[H3O+] = – log(0.20) = 0.70

The [HPO32–] may be determined from the second ionization constant.

400
 Chapter 17

[H2PO3–] [HPO32–] [H3O+]

I 0.20 – 0.20
C –x +x +x
E 0.20 – x +x 0.20 + x

 HPO 2−   H O + 
= 
3  3  = (x) (0.20 + x) = 2.0 × 10−7
Ka 2
 H PO  − (0.20 − x)
 2 3 

If we assume that x is small then 0.20 ± x ≈ 0.20. Then, x = [HPO32–] = 2.0 × 10–7 M.

 H O +   HC O − 
Ka =    2 4  = 6.0 × 10−2
+ –
3
17.109 H2C2O4 + H2O
H3O + HC2O4
[ H 2 C 2 O4 ]
[H2C2O4] [H3O+] [HC2O4–]
I 0.20 – –
C –x +x +x
E 0.20 – x +x +x

Ka =
( x )( x )
( 0.20 − x )
6.0 × 10–2 =
( x )( x )
( 0.20 − x )
–x2 – (6.0 × 10–2)x + (1.12 × 10–2) = 0
2

x=
(
− −6.0 × 10−2 ± ) ( −6.0 ×10 ) −2
(
− 4 ( −1) 1.12 ×10−2 ) = ( 6.0 ×10−2 ) ± (3.6 ×10−3 ) + ( 4.48 ×10−2 )
2 ( −1) −2

=
( 6.0 ×10 ) ± ( 2.20 ×10 )
−2 −1

−2
x = 8.0 × 10–2 = [H3O+], pH = 1.10

17.110 The hydrolysis equation is:

 HSO −  OH − 
Kb = 
2– – –
3  
SO3 + H2O
HSO3 + OH
SO 2 − 
 3 
In order to obtain Kb we will use the relationship Kw = Ka × Kb
K 1.0 × 10−14
Kb = w = = 1.5 × 10−7
Ka −8
6.6 × 10

[SO32–] [HSO3–] [OH–]

I 0.24 – –
C –x +x +x
E 0.24 – x +x +x
Since Kb is so small, assume that x << 0.24 and we determine x = 1.9 × 10–4 M = [OH–]
pOH = –log(1.9 × 10–4) = 3.72, pH = 14.00 – pOH = 10.28

401
 Chapter 17

[SO32-] = 0.24 M [HSO3-] = [OH-] = 1.9 x 10-4 M

[Na+] = 0.24 M

[H3O+] = 1.00 x 10-14/1.9 x 10-4 = 5.3 x 10-11

The second ionization is very small compared to the first ionization so the [HSO3-], [OH-] and [H3O+] do
not change significantly.

For the concentration of H2SO3

 −
H 2SO3  OH 
HSO3– + H2O
H2SO3 + OH– K b2 =
 HSO − 
 3 

Kw 1.0 × 10−14
K b2 = = = 8.3 × 10−13
K a1 1.2 × 10−2

H 2SO3  1.9 × 10−4 

K b2 =   = 8.3 × 10–13
1.9 ×10−4 
 
[H2SO3] = 8.3 × 10–13

17.111 The hydrolysis equation is:

 HCO −  OH − 
Kb = 
2– – –
3  
CO3 + H2O
HCO3 + OH
 CO 2− 
 3 

In order to obtain Kb we will use the relationship Kw = Ka × Kb

Kw 1.0 × 10−14
Kb1 = = = 1.8 × 10 −4
Ka2 −11
5.6 × 10

[CO32–] [HCO3–] [OH–]

I 0.33 – –
C –x +x +x
E 0.33 – x +x +x

1.8 × 10–4 =
( x )( x )
0.33 − x
Since Kb is so small, assume that x << 0.33 and we determine x = 7.7 × 10–3 M = [OH–]
pOH = –log(7.7 × 10–3) = 2.11, pH = 14.00 – pOH = 11.89
H 2 CO3  OH − 
–
HCO3 + H2O
H2CO3 + OH –
K b2 =  
 HCO − 
 3 
For the concentration of H2CO3
Kw 1.0 × 10−14
K b2 = = = 2.3 × 10−8
K a1 −7
4.3 × 10

402
 Chapter 17

H 2 CO3  7.7 × 10−3 

K b2 =   = 2.3 × 10–8
 7.7 × 10−3 
 
[H2CO3] = 2.3 × 10–8

17.112 C6H5O73– + H2O
HC6H5O72– + OH–

 HC H O 2−   OH − 
 6 5 7   Kw 1.0 × 10−14
Kb = = = = 2.5 × 10 −8
C6 H5 O7 3−  Ka3 4.0 × 10−7

[C6H5O73–] [HC6H5O72–] [OH–]

I 0.12 – –
C –x +x +x
E 0.12 – x +x +x

Assume x << 0.12

Kb =
( x )( x ) = 2.5 × 10−8 x = 5.5 × 10−5 = [OH − ]
0.12
pOH = 4.26 pH = 9.74

17.113 C2O42– + H2O
HC2O4– + OH–

 HC O −  OH − 
 2 4   K 1.0 × 10−14
Kb = = w = = 1.6 × 10−10
 C2 O 4 
2−
Ka 5.4 × 10 −5

[C2O42–] [HC2O4–] [OH–]

I 0.22 – –
C –x +x +x
E 0.22 – x +x +x

Assume x << 0.22

Kb =
( x )( x ) = 1.6 × 10−10 x = 5.9 × 10−6 = [OH − ]
0.22
pOH = 5.23 pH = 8.77

Kw 1.0 x 10−14
3–
17.114 PO4 + H2O
HPO4 + OH 2– – K b1 = = =2.4 × 10−2
Ka 3 4.2 x 10−13
Kw 1.0 x 10−14
2–
HPO4 + H2O
H2PO4 + OH – – Kb 2 = = =1.6 × 10−7
Ka 2 −8
6.2 x 10
Kw 1.0 x 10−14
–
H2PO4 + H2O
H3PO4 + OH – Kb 3 = = = 1.3 × 10−12
K a1 7.5 x 10−3

By analogy with polyprotic acids, we know that

[H2PO4–] = 1.6 × 10–7

403
 Chapter 17

We need to solve the first equilibrium expression to determine [HPO42–].

 HPO 2 −   OH − 
= 
4   = 2.4 × 10−2
K b1
 PO 3 −
 4 

[PO43–] [HPO42–] [OH–]

I 0.50 – –
C –x +x +x
E 0.50 – x +x +x
Assume x << 0.50

Kb1 =
( x )( x ) = 2.4 × 10−2
0.50 − x
Use the quadratic equation to solve for x since Kb is so large
x = 9.8 × 10–2 M = [OH–] = [HPO42–]
pOH = 1.01 pH = 12.99

[PO43–] = 0.50 – 9.8 × 10–2 = 0.40 M

Solve the third equilibrium expression to determine [H3PO4]:
H3 PO4  OH − 
K b3 =   = 1.3 × 10−12
 H PO − 
 2 4 
Substitute the calculated values of [H2PO4–] and [OH–] and solve for x:

K b3 =
(9.8 × 10 ) x = 1.3 × 10
−2
−12

(1.6 × 10 )
−7

x =  H3 PO4  = 2.1 × 10−18

17.115 Because the pH is so high and is greater than pKa, the [CO32–] = 0.10 M. The added OH– reacts with most
of the HCO3– to reform CO32–.

17.116 Since HCO2H and NaOH react in a 1:1 ratio:

HCO2H + NaOH
NaHCO2 + H2O

we can use the equation Va × Ma = Vb × Mb to determine the volume of NaOH that is required to reach the
equivalence point, i.e. the point at which the number of moles of NaOH is equal to the number of moles of
HCO2H:
VNaOH = 35.0 mL × 0.050/0.050 = 35.0 mL
Thus the final volume at the equivalence point will be 35.0 + 35.0 = 70.0 mL.
The concentration of NaHCO2 would then be:
0.035 mol/L × 0.050 L = 1.75 × 10–3 mol HCO2H = 1.75 × 10–3 mol NaHCO2
1.75 × 10–3 mol/0.070 L = 2.5 × 10–2 M NaHCO2

The hydrolysis of this salt at the equivalence point proceeds according to the following equilibrium:
HCO2– + H2O
HCO2H + OH–
[ HCO2 H] OH −

Kb = = 5.6 × 10−11
 HCO2 
−

404
 Chapter 17

[HCO2–] [HCO2H] [OH–]

I 0.025 – –
C –x +x +x
E 0.025 – x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression and assuming
x << 0.050 gives:

Kb =
( x )( x ) = 5.6 × 10−11
0.025

x2 = 1.4 × 10–12 x = 1.2 × 10–6 M = [OH–] = [HCO2H]

pOH = –log[OH ] = –log(1.2 × 10–6) = 5.93
–

pH = 14.00 – pOH = 14.00 – 5.93 = 8.07

Cresol red would be a good indicator, since it has a color change near the pH at the equivalence point.

17.117 Since HBr and NH3 react in a 1:1 ratio:

HBr + NH3
NH4+ + Br–
we can use the equation Va × Ma = Vb × Mb to determine the volume of HBr that is required to reach the
equivalence point, i.e. the point at which the number of moles of HBr is equal to the number of moles of
NH3:
VHBr = 25 mL × 0.12/0.12 = 25 mL
Thus the final volume at the equivalence point will be 25 + 25 = 50 mL.
The concentration of NH4+ would then be:
0.12 mol/L × 0.025 L = 3.0 × 10–3 mol NH3 = 3.0 × 10–3 mol NH4+
3.0 × 10–3 mol/0.050 L = 6.0 × 10–2 M NH4+

At the equivalence point NH4+ dissociate according to the following equilibrium:

NH4+
H+ + NH3

 NH3   H 
+

Ka = = 5.6 × 10−10
 NH 4+ 
 

[NH4+] [H+] [NH3]

I 0.060 – –
C –x +x +x
E 0.060 – x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression and assuming
x << 0.050 gives:

Ka =
( x )( x ) = 5.6 × 10−10
0.060

x = 5.8 × 10–6 M = [H+]

pH = –log[H+] = –log(5.8 × 10–6) = 5.24

Bromocresol purple would be a good indicator, since it has a color change near the pH at the equivalence
point.

405
 Chapter 17

 0.180 mol HC2 H3O2  –3

17.118 mol HC2H3O2 = (30.0 mL HC2H3O2)   = 5.40 × 10 mol HC2H3O2
 1000 mL HC H O
2 3 2 
 0.250 mol OH  −
mol OH– = (45.0 mL OH–)   = 1.13 × 10–2 mol OH–
 1000 mL OH − 
 
excess OH– = (1.13 × 10–2) – (5.4 × 10–3) = 5.9 × 10–3 mol

5.9 × 10−3 moles

[OH − ] = = 7.87 × 10–2 M
 1L 
(30.0 + 45.0 mL) 
 1000 mL 
pOH = 1.10
pH = 12.90

 0.200 mol HC2 H3O 2  –3

17.119 mol HC2H3O2 = (25.0 mL HC2H3O2)   = 5.00 × 10 mol HC2H3O2
 1000 mL HC H O
2 3 2 
 0.400 mol OH  −
mol OH– = (15.0 mL OH–)   = 6.00 × 10–3 mol OH–
 1000 mL OH − 
 
excess OH– = (6.00 × 10–3) – (5.00 × 10–3) = 1.00 × 10–3 mol

1.00 × 10−3 moles

[OH − ] = = 2.5 × 10–2 M
 1L 
(25.0 + 15.0 mL)  
 1000 mL 
pOH = 1.60
pH = 12.40

 H O +  C H O − 
Ka =    2 3 2  = 1.8 × 10−5
3
17.120 (a) HC2H3O2 + H2O
H3O+ + C2H3O2–
HC 2 H3O 2 

[HC2H3O2] [H3O+] [C2H3O2–]

I 0.1000 – –
C –x +x +x
E 0.1000 – x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression and
assuming that x << 0.1000 gives:
x = [H3O+] = 1.342 × 10–3 M.
pH = –log [H3O+] = –log (1.342 × 10–3) = 2.87.

(b) When NaOH is added, it will react with the acetic acid present decreasing the amount in solution
and producing additional acetate ion. Since this a one–to–one reaction, the number of moles of
acetic acid will decrease by the same amount as the number of moles of NaOH added and the
number of moles of acetate ion will increase by an identical amount. We must determine the
number of moles of all ions present and calculate new concentrations accounting for dilution.

 0.1000 moles HC 2 H3O 2  –3

mol HC2H3O2 = (0.07500 L solution)   = 7.500 × 10 mol HC2H3O2
 1 L solution 
 0.1000 moles OH −
mol OH– = (0.02500 L solution)   = 2.500 × 10–3 mol OH–
 1 L solution 
 

406
 Chapter 17

7.500 × 10−3 moles − 2.500 × 10−3 moles

HC 2 H3O 2  = = 5.000 × 10–2 M
0.07500 L + 0.02500 L
−3
C H O −  = 0 moles + 2.500 × 10 moles = 2.500 × 10–2 M
 2 3 2  0.07500 L + 0.02500 L
C H O − 
pH = pK a + log 
2 3 2 

HC2 H3O2 

= 4.7447 + log
( 2.500 × 10 ) = 4.44
−2

(5.000 × 10 )−2

(c) When half the acetic acid has been neutralized, there will be equal amounts of acetic acid and
acetate ion present in the solution. At this point, pH = pKa = 4.74.

(d) At the equivalence point, all of the acetic acid will have been converted to acetate ion. The
concentration of the acetate ion will be half the original concentration of acetic acid since we have
doubled the volume of the solution. We then need to solve the equilibrium problem that results
when we have a solution that possesses a [C2H3O2–] = 0.05000 M.
C2H3O2– + H2O
HC2H3O2 + OH–

HC2 H3O2   OH − 
Kb =   = 5.6 × 10−10
C H O − 
 2 3 2 

[C2H3O2–] [HC2H3O2] [OH–]

I 0.05000 – –
C –x +x +x
E 0.05000 – x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression and
assuming that x << 0.05000 gives: x = [OH–] = 5.292 × 10–6 M.
pOH = –log [OH–] = –log (5.292 × 10–6) = 5.2764.
pH = 14.0000 – pOH = 14.0000 – 5.2764 = 8.72.

17.121 (a) NH3 + H2O
NH4+ + OH–

 NH +  OH − 
Kb = 
4   = 1.8 × 10−5
NH3 

[NH3] [NH4+] [OH–]

I 0.1000 – –
C –x +x +x
E 0.1000 – x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression and
assuming that x << 0.1000 gives:
x = [OH–] = 1.342 × 10–3 M.
pOH = –log [OH–] = –log (1.342 × 10–3) = 2.8724.
pH = 14.00 – pOH = 11.1276

407
 Chapter 17

(b) When HCl is added, it will react with the ammonia present decreasing the amount in solution and
producing additional ammonium ion. Since this a one–to–one reaction, the number of moles of
ammonia will decrease by the same amount as the number of moles of HCl added and the number
of moles of ammonium ion will increase by an identical amount. We must determine the number
of moles of all ions present and calculate new concentrations accounting for dilution.

 0.1000 moles NH3  –3

mol NH3 = (0.05000 L solution)   = 5.000 × 10 mol NH3
 1 L solution 
 0.1000 moles H + 
mol H+ = (0.02000 L solution)   = 2.000 × 10–3 mol H+
 1 L solution 
 
5.000 × 10−3 moles − 2.000 × 10−3 moles
 NH3  = = 4.286 × 10–2 M NH3
0.05000 L + 0.02000 L
−3
 NH +  = 0 moles + 2.000 × 10 moles = 2.857 × 10–2 M NH4+
 4  0.05000 L + 0.02000 L
 NH +  (
2.857 × 10−2 ) = 4.5686
pOH = pKb + log 
4 
= 4.7447 + log
NH3  (
4.286 × 10−2 )
pH = 14.0000 – pOH = 9.4314

(c) When half the ammonia has been neutralized, there will be equal amounts of ammonia and
ammonium ion present in the solution. At this point, pH = pKb = 4.7447.

(d) At the equivalence point, all of the ammonia will have been converted to ammonium ion. The
concentration of the ammonium ion will be half the original concentration of ammonia since we
have doubled the volume of the solution. We then need to solve the equilibrium problem that
results when we have a solution that possesses a [NH4+] = 0.05000 M.

NH4+
H+ + NH3
 H +   NH 
 3
Ka =   = 5.6 × 10−10
 NH + 
 4 

[NH4+] [H+] [NH3]

I 0.05000 – –
C –x +x +x
E 0.05000 – x +x +x

Substituting the above values for equilibrium concentrations into the mass action expression and
assuming that x << 0.05000 gives:
x = [H+] = 5.292 × 10–6 M.
pH = –log [H+] = –log (5.292 × 10–6) = 5.2764.

Additional Exercises

17.122 HNO2 + H2O
H3O+ + NO2–

[H3O+ ][NO 2− ]
Ka = = 7.1 × 10−4
 HNO 2 

408
 Chapter 17

[HNO2] [H3O+] [NO2–]

I 1.0 – –
C 1.0 – x +x +x
E 1.0 – x +x +x

Assume x << 1.0

[x][x]
Ka = = 7.1 × 10−4
[1.0]
x = 2.7 × 10–2 = [H3O+]

% ionization = ([H+]/[total acid]) × 100% = (2.7 × 10–2/1.0) × 100% = 2.7%

At lower concentrations, the only change is the denominator in the final

expression for Ka above. Calculating the answers, we have:

1.0 M = 2.7% ionization

0.10 M = 8.4% ionization
0.010 M = 27% ionization

As a weak acid becomes more dilute, its % ionization goes up.

17.123 From the complete ionization of HCl: [H+] = 0.100 M

We must solve an equilibrium problem in order to determine the contribution of H+ from the acetic acid.
 H +  C H O − 
Ka =   
2 3 2 
+
HC2H3O2
H + C2H3O2 –
= 1.8 × 10−5
HC2 H3O 2 

[HC2H3O2] [H+] [C2H3O2–]

I 0.125 0.100 –
C –x +x +x
E 0.125–x 0.100+x +x

Substituting the above values for equilibrium concentrations into the mass action expression and assuming
that x << 0.125 M and x << 0.100 M gives:
x = [C2H3O2–] = 2.25 × 10–5 M.
The total [H+] is therefore 0.100 + 2.25 × 10–5 = 0.100 M, and pH is 1.000. The weak acid contributes very
little H+ to the final solution.

17.124 When these two solutions are mixed, the HCl will react with the ammonia producing NH4+. Since HCl is
the limiting reactant, we will have an excess of ammonia. The resulting solution will be a buffer as it
consists of ammonia, a weak base, and ammonium ion, its conjugate acid.

We need to determine the amount of NH4+ that is produced and the amount of NH3 that remains:
 0.500 mol HCl   1 mol H 
+
mol H + = (225 mL HCl)     = 0.1125 mol H +
 1000 mL HCl   1 mol HCl 

mol NH3 = (mol NH3)initial – (mol H+)added
 0.500 mol NH3  +
mol NH3 = (375 mL)   – 0.1125 mol H = 0.075 mol NH3
 1000 mL NH 3 
mol NH4+ = mol H+ = 0.1125 mol NH4+

409
 Chapter 17

 NH + 
pOH = pK b + log 
4 
= 4.74 + 0.18 = 4.92
 NH3 
pH = 14.00 – pOH = 9.08

17.125 (a) We first need to determine the concentration of the components of the solution.
mol HC2 H3O 2  12.5 g HC2 H3O 2   1 mol HC2 H3O 2 
HC2 H3O2  = =   = 0.269 M
L soln  0.775 L   60.05 g HC2 H3O 2 
mol NaC2 H3O 2  20.0 g NaC2 H3O 2   1 mol NaC2 H3O 2 
 NaC2 H3O2  = =   = 0.315 M
L soln  0.775 L   82.03 g NaC2 H3O 2 

pH = pK a + log
[ anion ] = 4.745 + log 0.315 = 4.813
[ acid ] 0.269
(b) The added base will react with the acid present using it up and producing additional acetate ion.
To solve this problem, determine the number of moles of base added and subtract this amount
from the amount of acid present. Add the same amount to the amount of acetate ion present. Be
sure to account for dilution when you determine the new concentrations.

 0.25 mol NaOH   1 mol OH 

−
mol OH − = (25.00 mL NaOH)     = 0.0063 mol OH–
 1000 mL NaOH   1 mol NaOH 
Consequently, the # mol of acetic acid will decrease by 0.0063 and the # of moles of acetate ion
will increase by 0.0063. The new concentrations are:
mol HC2 H3O 2  ( 0.208 − 0.0063) mol HC2 H3O 2 
HC2 H3O2  = =
  = 0.252 M
L soln  0.800 L 
−  0.244 + 0.0063) mol C H O − 
C H O −  = mol C2 H3O 2 =  ( 2 3 2  = 0.313 M
 2 3 2  L soln  0.800 L 
 

pH = pK a + log
[ anion ] = 4.745 + log 0.313 = 4.839
[ acid ] 0.252

(c) This problem is identical to the previous except that we are adding acid to the original solution.
Consequently, the acid concentration will increase and the acetate ion concentration will decrease.
 0.40 mol HCl   1 mol H 
+
mol H + = (25.0 mL HCl)     = 0.010 mol H+
 1000 mL HCl  1 mol HCl 

mol HC2 H3O 2  ( 0.208 + 0.010 ) mol HC2 H3O 2 
HC2 H3O2  = L soln
=
 0.800 L
 = 0.273 M
 
−  0.244 − 0.010 ) mol C H O − 
C H O −  = mol C2 H3O 2 =  ( 2 3 2  = 0.293 M
 2 3 2  L soln  0.800 L 
 

pH = pK a + log
[ anion ] = 4.745 + log 0.293 = 4.776
[ acid ] 0.273

17.126 (a) The equation that will be used is the normal Henderson–Hasselbach equation, namely:
A− 
pH = pK a + log
[ anion ]
= pK a + log  
[ acid ] [ HA ]

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 Chapter 17

where A– = C2H3O2– and HA = HC2H3O2. We note further that the log term involves a ratio of
concentrations, but that the volume remains constant in a process such as that to be analyzed here.
Thus the log term may be replaced by a ratio of mole amounts, since volumes cancel:

pH = pK a + log
( moles C H O )
2 3 2
−

( moles HC2 H3O2 )

Thus we need only determine the number of moles of acid and conjugate base that remain in the
buffer after the addition of a certain amount of H+ or OH–, in order to determine the pH of the
buffer mixture after that addition.

The buffer is changed in the following way by the addition of OH–:

HC2H3O2 + OH–
H2O + C2H3O2–
In other words, if 0.0100 moles of OH– are added to the buffer, the amount of HC2H3O2 goes
down by 0.0100 moles, whereas the amount of C2H3O2– goes up by 0.0100 moles. In addition, the
pH of the solution will increase upon the addition of base.
The buffer is changed in the following way by the addition of H+:
C2H3O2– + H+
HC2H3O2
If 0.0100 mol of H+ are added, then the amount of C2H3O2– goes down by 0.0100 moles and the
amount of HC2H3O2 goes up by 0.0100 moles. As before, the addition of acid will decrease the
pH of the buffer system.

For the general buffer mixture that contains x mol of C2H3O2– and y mol of HC2H3O2, we can
apply the Henderson–Hasselbach equation, noting the maximum amount by which we want the
pH to change (namely 0.10 units):

For the case of added base:

( x + 0.0100 ) moles C2 H3O2−

5.12 + 0.10 = 4.74 + log
( x − 0.0100 ) moles HC2 H3O2
Simplifying and taking the antilog of both sides of the above equation gives: [x + 0.0100]/[y –
0.0100] = 3.0, which is now designated eq. 1.

For the case of added acid:

( x − 0.0100 ) moles C2 H3O2−

5.12 − 0.10 = 4.74 + log
( x + 0.0100 ) moles HC2 H3O2
Simplifying and taking the antilog of both sides of the equation gives:
[x – 0.0100]/[y + 0.0100] = 1.9, which is now designated eq. 2.

The equations 1 and 2 as designated above are solved simultaneously, since they are two equations
containing two unknowns:

x = initial mol C2H3O2– = 0.15 mol

y = initial mol HC2H3O2 = 6.3 × 10–2 mol

These values are converted to grams as follows:

6.3 × 10–2 mol HC2H3O2 × 60.1 g/mol = 3.8 g HC2H3O2
0.15 mol NaC2H3O2 × 118 g/mol = 18 g NaC2H3O2•2H2O

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 Chapter 17

These are the minimum amounts of acid and conjugate base that would be required in order to
prepare a buffer that would change pH by only 0.10 units on addition of either 0.0100 mol of OH–
or 0.0100 mol of H+.

(b) 6.3 × 10–2 mol/0.250 L = 0.25 M HC2H3O2

0.15 mol C2H3O2–/0.250 L = 0.60 M NaC2H3O2

(c) 0.0100 mol OH–/0.255 L = 3.92 × 10–2 M OH–

pOH = –log[OH–] = –log(3.92 × 10–2) = 1.406
pH = 14.000 – pOH = 14.000 – 1.406 = 12.593

(d) 1.00 × 10–2 mol H+/0.255 L = 3.92 × 10–2 M H+

pH = –log[H+] = –log(3.92 x 10–2) = 1.406

17.127 Since the ammonium ion is the salt of a weak base, NH3, it is acidic. The fluoride ion is the salt of a weak
acid, HF, so it is basic. In order to determine if the solution is acidic or basic, we need to determine the
relative strength of the two components. Use the relationship Ka × Kb = Kw in order to determine the
dissociation constants for the cyanide ion and the ammonium ion.

Ka(NH4+) = Kw ÷ Kb(NH3) = 1.0 × 10–14 ÷ 1.8 × 10–5 = 5.6 × 10–10

Kb(F–) = Kw ÷ Ka(HF) = 1.0 × 10–14 ÷ 6.8 × 10–4 = 1.5 × 10–11

Since the Ka(NH4+) is larger than the Kb(F−) the NH4F solution will be acidic.

17.128 Using the equilibrium for the conjugate base of NH4+ (Kb = 1.8 × 10–5) and the conjugate acids of C2H3O2–
(Ka = 1.8 × 10–5). Since the two equilibrium constants are equivalent, and the concentrations of the anion
and cation are equivalent, therefore the concentrations of H+ and OH– are equivalent and the pH is 7.

17.129 In order to solve this problem we must first neutralize the HNO3 that is present in the solution. Since
HNO3 is a monoprotic acid and NH3 is a monobasic base, they will react in a one to one stoichiometry. For
every mole of NH3 added, one mole of HNO3 will be neutralized and one mole of NH4+ will be produced.
There are initially 0.0125 moles HNO3 = (0.250 L)(0.050 mol L–1) present in the solution. Consequently,
we must first add 0.0125 moles of NH3 to neutralize all of the HNO3.

Now the question may be rephrased to ask, how much ammonia should be added to a solution that is 0.050
M in NH4+ so that the final pH is 9.26?

[NH3] [NH4+] [OH–]

I Z 0.050 –
C Z–x 0.050 + x +x
E Z–x 0.050 + x +x

Kb =
( 0.050 + x )( x ) = 1.8 × 10−5
(Z − x)
The problem states that the equilibrium pH = 9.26 and, therefore, the pOH = 4.74 which implies that [OH–]
= 1.8 × 10–5 M = x. Substituting this into the equilibrium expression and assuming that Z >> x we get

( 0.050 ) (1.8 × 10−5 )

= 1.8 × 10−5
Z
and Z = 0.050 M. Since the volume of the solution is 250 mL, this concentration corresponds to 0.0125
moles NH3 = (0.250 L)(0.050 mol L–1).

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 Chapter 17

The total amount of NH3 that must be added to the original solution is thus
0.0125 moles + 0.0125 moles = 0.0250 mols. The first addition neutralizes the HNO3 and the second
amount adjusts the pH.

The volume of NH3 that must be added may be calculated using the ideal gas law;

V =
nRT
=
(L atm (298 K)
(0.0250 mol) 0.0821 mol K )= 0.63 L = 630 mL
P 1 atm
(
(740 torr) 760 torr )

17.130 Both HClO4 and HNO3 are 100% ionized in water and, therefore, appear to be the same strength. To
distinguish between these two, we would need a solvent that is a weaker proton acceptor than H2O.

17.131 (a) HSO4– + H2O
H3O+ + SO42–

SO 2−   H O + 
Ka = 
4  3  = 1.2 × 10–2
[ HSO4 ]
(b)
[HSO4–] [H3O+] [SO42–]
I 0.010 – –
C –x +x +x
E 0.010 – x +x +x

[x][x]
Ka = = 1.2 × 10−2
0.010 − x
Solve the quadratic equation to get x = 6.5 × 10–3 = [H3O+]

[x][x]
(c) Ka = = 1.2 × 10−2 x = 1.1 × 10 −2 = [H3O+ ]
0.010

(d) The exact answer (obtained in part b) is 60% smaller than the approximate solution.

17.132 Ascorbic acid has the formula H2C6H6O6 and is a diprotic weak acid. We only need look at the first
dissociation to determine the pH.
 HC H O −   H + 
K a1 = 
– +
6 6 6   = 8.0 × 10−5
H2C6H6O6
HC6H6O6 + H
H 2 C6 H 6 O6 
 6.0 g H 2 C6 H 6 O6   1 mole H 2 C6 H 6 O6   1000 mL 
H 2 C6 H 6 O6  =     = 0.14 M
 250 mL   176 g H 2 C6 H 6 O6   1 L 

[H2C6H6O6] [HC6H6O6–] [H+]

I 0.14 – –
C –x +x +x
E 0.14 – x +x +x

 HC H O −   H + 
Ka 1 = 
6 6 6   = (x)(x) = 8.0 × 10−5
 2 6 6 6 
H C H O (0.14 − x)

413
 Chapter 17

Assuming that x << 0.14 and solving we find;

x = [H+] = 3.3 × 10–3 M pH = – log[H+] = – log (3.3 × 10–3) = 2.47

17.133 This exercise is an example of a titration using a strong acid and a strong base. Prior to reaching the
equivalence point, there will be an excess of acid present. The amount of acid present may be determined
by subtracting the number of moles of base added from the amount of acid initially present. We may then
use the dilution equation, M1 × V1 = M2 × V2, to determine the new concentration of acid and then calculate
the pH. After the equivalence point, there is an excess of base. The amount in excess is determined by
subtracting the inital amount of acid present from the amount of base added. Again, the dilution equation
may be used to determine the resulting concentration.

Start by determining the amount of H+ initially present:

 0.1000 moles H + 
moles H + = ( 25.00 mL solution )  
 1000 mL solution 
 
= 2.500 × 10−3 moles H +

(a) Initially, there is only 0.1000 M HCl present: [H+] = 0.1000 M,

pH = –log[H+] = 1.0000.

(b) 10.00 mL added base

 0.1000 moles OH − 
moles OH − = (10.00 mL solution )   = 1.000 × 10–3 mol OH–
 1000 mL solution 
 
−3 −3
H  =
+ 2.500 × 10 moles − 1.000 × 10 moles
  0.02500 L + 0.01000 L = 4.286 × 10–2 mol H+

pH = –log[H+] = 1.3680

(c) 24.90 mL added base

 0.1000 moles OH − 
moles OH − = ( 24.90 mL solution )   = 2.490 × 10–3 mol OH–
 1000 mL solution 
 
−3 −3
 H +  = 2.500 × 10 moles − 2.490 × 10 moles = 2.004 × 10–4 mol H+
  0.02500 L + 0.02490 L
pH = –log[H+] = 3.6981

(d) 24.99 mL added base

 0.1000 moles OH − 
moles OH − = ( 24.99 mL solution )   = 2.499 × 10–3 mol OH–
 1000 mL solution 
 
−3 −3
 H +  = 2.500 × 10 moles − 2.499 × 10 moles = 2.000 × 10–5 mol H+
  0.02500 L + 0.02499 L
pH = –log[H+] = 4.6989

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 Chapter 17

(e) 25.00 mL added base

This is the equivalence point and [H+] = 1.000 × 10–7 M

pH = 7.000

(f) 25.01 mL added base

We have now added excess base so we will subtract the number moles H+ initially present from
the number moles OH– added.
 0.1000 moles OH − 
moles OH − = ( 25.01 mL solution )   =2.501 × 10–3 mol OH–
 1000 mL solution 
 
−3 −3
OH −  = 2.501 × 10 moles − 2.500 × 10 moles = 2.000 × 10–5 M OH–
  0.02501 L + 0.02500 L
pOH = –log[OH–] = 4.6991
pH = 14.0000 – pOH = 9.3009

(g) 25.10 mL added base

 0.1000 moles OH − 
moles OH − = ( 25.10 mL solution )   =2.510 × 10–3 mol OH–
 1000 mL solution 
 
−3 −3
OH −  = 2.510 × 10 moles − 2.500 × 10 moles = 1.996 × 10–4 M OH–
  0.02510 L + 0.02500 L
pOH = –log[OH–] = 3.6998
pH = 14.0000 – pOH = 10.3002

(h) 26.00 mL added base

 0.1000 moles OH − 
moles OH − = ( 26.00 mL solution )   =2.600 × 10–3 mol OH–
 1000 mL solution 
 
−3 −3
OH −  = 2.600 × 10 moles − 2.500 × 10 moles = 1.961 × 10–3 M OH–
  0.02600 L + 0.02500 L
pOH = –log[OH–] = 2.708
pH = 14.0000 – pOH = 11.292

(i) 50.00 mL added base

 0.1000 moles OH − 
moles OH − = ( 50.00 mL solution )   = 5.000 × 10–3 mol OH–
 1000 mL solution 
 
−3 −3
OH −  = 5.000 × 10 moles − 2.500 × 10 moles = 3.333 × 10–2 M OH–
  0.05000 L + 0.02500 L
pOH = –log[OH–] = 1.4771
pH = 14.0000 – pOH = 12.5229

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 Chapter 17

17.134 For the given mixture, pH does not equal pKa because the concentration of the acid does not equal the
concentration of its salt.
For each OH– ion added an additional F– will form and an HF molecule will dissociate:
HF + H2O
H3O+ +F–
As OH– is added it reacts with the H3O+ causing additional HF to dissociate. For each H+ ion added an F–
ion will react with it forming additional HF. Using the equation above, the added H+ reacts with F–
producing HF.

Initially, there are 5HF and 4F − ions. After addition of 3OH − ions we will have 2HF and 6F −. If 2H+ are
added we will have 7HF and 2F −.

Multi-Concept Problems

17.135 A solution with pH = 4.00 would have:

[H+] = 10–pH = 10–4.00 = 1.00 × 10–4 M

= 1.00 × 10–4 mol [H+]/L solution
= 0.000100 mol [H+]/L solution
We begin with:
 1 L HCl soln   0.010 mol HCl 
mol HCl = 200 mL HCl soln   
 1,000 mL HCl soln   1 L HCl soln 
= 0.002 mol HCl
= 0.002 mol H+

Our final molarity will be: M = mol [H+] /L solution. This can be written as:
M = (0.002 – nNaOH)/(0.200 + x),
where nNaOH = moles of NaOH added and, x = volume of 0.10 M NaOH added.

But nNaOH is simply MNaOH·VNaOH, so

M = (0.002 – 0.10x)/(0.200 + x)
0.000100 = (0.002 – 0.10x)/(0.200 + x)
(0.200 + x)0.000100 = (0.002 – 0.10x)

416
 Chapter 17

2.00 × 10−5 + 0.000100 x = 0.002 – 0.10x

0.1001 x = 0.00198
x = 0.0200, or 20.0 mL
20.0 mL of 0.10 M NaOH should be added to 200 mL of 0.010 M HCl

17.136 pOH = 14.00 – pH = 14.00 – 10.08 = 3.92

pOH = –log [OH–]
[OH–] = 10–pOH = 10–3.92 = 1.2 × 10–4 M

1 Tbs has a volume of 14.8 mL

 1.2 × 10−4 mol   1 mol Mg(OH) 2   58.32 g Mg(OH)2 

grams Mg(OH) 2 = (29.6 mL)  
 1000 mL   2 mol OH −   1 mol Mg(OH)2 
 
= 1.0 × 10−4 g Mg(OH)2

17.137 First, we must find the concentration of the HCl solution. Since HCl is a strong acid, we know that [HCl] =
[H+]. We can find [H+] from the pH:
[H+] = 10–pH = 10–2.15 = 7.1 × 10–3 M H+

Now we can solve the problem using the given conversion factors:
 7.1 × 10−3 mol H +   1 mol OH –   1000 mL OH – 
volume of 0.0100 M KOH = 325 mL    
 1000 mL solution   1 mol H +   0.0100 mol OH – 
= 231 mL 0.0100 M KOH

17.138 pOH = 14 – pH = 14 – 12.05 = 1.95

[OH–] = 10–pOH = 10–1.95 = 1.12 × 10–2 M OH–
 1.1× 10−2 mol OH –  1 mol H + 
mol of H+ = 30.0 mL LiOH solution    = 3.4 × 10–4 mol H+
 1000 mL LiOH solution  1 mol OH – 
  
 3.4 × 10 mol H 
–4 +
–2
M HNO3 =   = 1.5 × 10 M HNO3
 0.02275 L solution 

17.139 HCl and NaOH react in a one-to-one mole ratio. The first step is to determine the limiting reagent.

Moles HCl = 38.0 mL x (1L/1000 mL) x 0.000200 M = 7.6 x 10-6 moles

Moles NaOH = 40.0 mL x (1 L.1000 mL) x 0.000180 M = 7.2 x 10-6 moles

The final solution will have an excess of H+.

7.6 x 10-6 mol H+ - 7.2 x 10-6 mol OH− = 4.0 x 10-7 mol H+

[H+] = 4.0 x 10-7 mol/(0.0380 + 0.040) L = 5.1 x 10-6 M

pH = -log (5.1 x 10-6) = 5.29

17.140 The moles of HCl is determined from the ideal gas law:

n=
(
1 atm
)
PV ( 734 torr ) 760 torr ( 0.0100 L )
= = 3.947 × 10 –4 mol HCl
RT L atm
0.0821 mol K 298 K

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 Chapter 17

The molarity of the solution is:

3.95 × 10 –4 mol HCl
M of solution = = 1.54 × 10–3 M HCl
0.257 L solution
pH = –log[H+] = –log(1.54 × 10–3 M) = 2.813

17.141 From problem 17.140, we find there are 3.95 × 10–4 mol HCl present. We need to know how many mol
NaOH are in the NaOH solution to react with the HCl. We can find [OH–] from the given pH:

pOH = 14.00 – pH = 14.00 – 10.50 = 3.50

[OH–] = 10–pOH = 10–3.50 = 3.16 × 10–4 M
 1 L NaOH soln   3.16 × 10 mol NaOH 
–4
mol NaOH = 20.00 mL NaOH soln    
 1000 mL NaOH soln   1 L NaOH soln 

–6
= 6.32 × 10 mol NaOH

Since HCl and NaOH react in a 1–to–1 ratio, 6.32 × 10–6 mol of each will neutralize one another. This
leaves (3.95 × 10–4 mol HCl – 6.32 × 10–6 mol HCl) = 3.89 × 10–4 mol HCl remaining.

The concentration of H+ is now:

[H+] = mol H+/L solution

= 3.89 × 10–4 mol/0.0200 L solution
= 1.94 × 10–2 M

Therefore pH = –log [H+] = –log [1.94 × 10–2] = 1.71

17.142 Recall the ∆Tf = Kf m, where Kf is the molal freezing point depression constant for the solvent and m is the
molality of the solution. We need to determine the molality of this solution. In order to do this, we need to
determine the concentrations of the ions which result from the dissociation of the weak acid. Recall that
each ion in the solution helps to lower the freezing point.

HC2HO2Cl2  H+ + C2HO2Cl2–
 H +  C HO Cl − 
Ka =   
2 2 2 
= 5.0 × 10−2
[ HC2 HO2 Cl2 ]
[HC2HO2Cl2] [H+] [C2HO2Cl2–]
I 0.50 – –
C –x +x +x
E 0.50 – x +x +x

Ka =
( x )( x ) = 5.0 × 10−2
( 0.50 − x )
Because the value of Ka is relatively large, we must solve a quadratic equation in order to determine the H+
concentration. Doing so gives:

x = 0.14 M = [H+] = [C2HO2Cl2–]

[HC2HO2Cl2] = 0.50 – x = 0.36 M

We now calculate the molality of the components of the solution. Because this is an aqueous solution with
a density of 1.0 g/mL, the molality and the molarity have the same value: mH+ = 0.14, mC2HO2Cl2– = 0.14 and
mHC2HO2Cl2 = 0.36.

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 Chapter 17

The total molality is 0.14 + 0.14 + 0.36 = 0.64 m.

The freezing point depression constant for water equals –1.86 °C/m.

( )
∆Tf = −1.86 o C / m ( 0.64 m ) = −1.19 o C .

The freezing point of the solution is –1.19 °C.

In solving this problem, we are assuming that the dichloroacetic acid that does not dissociate does not
interact with other dichloroacetic acid molecules. In reality, there is some association between the acid
molecules forming dimers through hydrogen bonding.

If all of the undissociated acid formed dimmers then the molality of the solution would be:

m = 0.14 + 0.14 + 0.18 = 0.46 m.

Then ∆Tf = − 0.86 oC.

All of the dichloroacetic acid molecules do not form dimmers. Therefore, the freezing point depression
should be between − 0.86 oC and − 1.19 oC.

419